Documente Academic
Documente Profesional
Documente Cultură
CHEMISTRY
OF
FULLE S
This page is intentionally left blank
Advanced Series in
~ ~ ~ 1 E R E ~ E ~
Vol. 4
THE
CHEMISTRY
FULLERENS
edited by
R Taylor
University of Sussex, UK
World Scientific
Singapore. NewJersey*London*HongKong
Published by
World Scientific PublishingCo. Re. Ltd.
P 0 Box 128, F m r Road, Singapore9128
USA oflce: Suite IB, 1060Main Street, River Edge,NJ 07661
UK o%ce: 57 Shelton Street, Covent Garden, London WC2H 9HB
For phot~opyingof material in this volume, please pay a copying fee through the Copyright
Clearance Center, Inc., 222 Rosewood Drive, Danvers, Massachusetts 01923, USA.
ISBN: 981-02-2304-8
Printed in Singapore.
Foreword
Carbon must surely have been the first pure element (in the form of charcoal
p r o d u d by natural fires) that early man would have been aware of. It is therefore
astoniehieg that it should be possibly the last element to reveal that it has a new (in this
case third) form.
The story of how it was recorplised as a result stimulated by an interest in the
chemistry of the cosmos is now so well known as to need no firther elaboration here.
The latcan#ls of its discovtry by no means reflects incompetence or lack of observation
and a w a m m by earlier scientists, but rather the need for sophisticated instmmentation
that hu only recently become available (and not widely availabIe at that). In this book
you will read about some of the great technical ingenuity that is being used by some of
the thoussnds of scientists worldwide in the race (for it is no less than that) to uncover
the seotsts that this third form may reveal.
Thc discovery of the fullerenes with their geodesic structures (the name comes
from tb fbct that the American architect, R. BuckminsteAller was pre-cminent in
publidsing the geodesic architectural form) has been widely described as one of the
scieasifio discoveries of the XXth century. It has certainly captured the imagination of
sciontisrs in a manner possibly without precedent. At the time of writing, and only four
years since the first pure materials were isolated, over 3,500 papers on fullerenes have
been poblihed (three new papers appear every day) and hundreds of patents filed. A
whole new field of science, and especially of organic/organometallic chemistry (the
growtharea to come) has been born It is really too early to be confident of predicting
uses for this material, but superconductors, optical limiters, polymers, additives for
photowxlucting polymers, transfer reagents, electrical storage devices, and inhibitors of
enzymss in relation to the HIV virus feature amongst the possibilities so far considered
or investigeted.
This book is not intended to give an exhaustive coverage, nor could it given the
hectic pace of discovery. But the main principles of the chemical behaviour of the
fillemaea (at least of c60, or [bO]fbllerene as it will in hture be known) are now
sufl8cicatly established to make publication of this book timely The book begins with a
brief iutmduction, followed by a description of nomenclature, something that will
becorn of increasing importance as the chemistry develops This is followed by a survey
of the methods of making fidlerenes, description of how to isolate and purify them, and
their b d c properties. Chapters then describe each of the main types of reaction that the
fullemnee undergo. It is the intention that anyone wishing to enter this exciting field will
find all the key information within this book and will then be sufficiently equipped to
enter the fray.
In conclusion I would like to thank all of the contributors for producing their
manuhpta when there are so many other demands upon their time in this intensely
competitive field. I feel sure this book will be an important reference source for some
time to come.
R. Taylor
Sussex, January, 1995
V
This page is intentionally left blank
CONTENTS
Foreword V
vii
viii
Photopolymerization 188
Ynamines 189
Enones 190
Conclusions 191
The description 'third form of carbon' is a little misleading: third forms would be
more accurate since there are, in principle, an infinite number of Wlerenes possible. A
general understanding of the term fillerene is that it describes a closed cage molecule
comprised entirely of s&t-hybridised carbons arranged in hexagons and pentagons, and
of the latter there are always twelve as a consequence of Euler's theorem. The fillerene
comprised of twelve pentagonal rings is C20 (or [20]fillerene).
There can be any number of hexagons (except one)' and for each hexagon
present two extra carbon atoms are needed. Thus C6o ([60]fillerene), the most
acoessible (but not necessarily the most stable fillerene), contains twelve pentagons and
twenty hexagons. The definition can be widened to include molecules with heptagonal
rings, and in this case to close the cage requires an additional pentagon or each
heptagon present.2 Since heptagons in the structure produce a concave region in the
surfhe, to close the cage without undue strain requires a large cage. So if heptagon-
containing Werenes are found, they will probably be rather large, possibly containing
more than 100 carbon atoms. It is also possible to have a closed cage containing a
c o m b d o n of octagons, hexagons, and squares, derived fiom a regular fbllerene by
replacing two pentagons by squares, and two adjacent hexagons by an octagon, as for
example in octahedral C48.3Closed cages containing other than 5- and 6-membered
rings are known as qw+lllerenes.
Hitherto, the fillerenes have been referred to generally by their molecular
formula, e.g. C60, C70 etc. However, now that derivatisationis becoming commonplace,
as will be evident fiom reading the chapters in this book, it is necessary to introduce a
proper nomenclature term, since one cannot refer to methylc60 etc. A system similar to
that uetd with the annulenes is being adopted by IUPAC, and in this C6o is written as
[6O]firtlerene. As in the case of the annulenes, the number in square brackets indicates the
number of atoms and dso the number of n-electrons. (Note that the overall number of
bonds in a hllerene C, is 3n/2.) This method has been introduced too late for it to have
been incorporated in all of the chapters of this book, but it appears in some. For quasi-
fillerenes, the sizes of rings present are indicated in curved brackets in front of the name.
Thus octahedral C48 is described as (4,6,8)[48-oh]qumi-f%llerene.
It is just over four years since pure [60]fillerene (Fig. 1) and [70]fUerene (Fig.
2) were first isolated and characterised.4.5At that time it was widely assumed that these
1
2
molecules, and [60]fbllerene in particular would be very unreactive. This was based upon
the fact that this molecule has 12,500 resonance structures.6 However, all but one of
these involves the presence of a double bond in at least one pentagonal ring. This is a
destabiiising feature because strained five-membered rings adjacent to benzenoid rings
tend to avoid having a double bond in the pentagonal ring, for to do so would increase
the main in an already-strained ring; this latter is the basis of the long-known Mills-
Nixon effect.7 The heats of formation of [60]-and [7O]fbllerene are respectively 10.15
and 9.34 kcal/moIe* (which makes then thermodynamically much less stable than either
diamond or graphite), and this is consistent with the expectation that stability will
increase as the fullerene surface becomes more planar, which it will do with incrersing
size (at least for near spherical cages). Approximately 80% of this heat of formation is
due to strain, and to add a double bond to a pentagon increases the strain by cu. 8
kdrnole.
1. Addition Patterns
Some of the major addition patterns for [60]fillerene are now apparent; patterns
for [70]fidlerene are just emerging. The patterns can be categorised according to the
extent of eclipsing steric hindrance that exists,betweenthe addends:
1.1 Groups with no Eclipsing Steric Hindrance. These groups bridge two adjacent
carbon atoms. They may be small e.g. 0, CH2, medium sized, e.g. benzyne and cyclo-
pentadiene, or large, e.g. CPh2, Pt(PEt3)2. The latter group has been shown to undergo
six-fold addition to [60]fUllerene, the addends being disposed octahedrally.12 The
octahedral array not only avoids steric interactions between the components of the
addend, but creates a product which has eight benzenoid rings in which the restriction on
delocaliation, present in [60]fullerene, is partly removed (Fig. 3); the structure is thereby
greatly stabilised.13The greater delocalisation in these benzenoid rings is shown by the
bond lengths of 1.42 and 1.39 4 i.e. bond alternation is greatly reduced compared to
that in the original [60]hllerene. (It is probably generally the case that provided no
severe steric interactions are introduced by a given addition, and a substantial number of
free hexagons remain, then the derivatives will be more stable than the parent fullerene.)
Six-fold addition has been shown to take place with CPh2.14 benzyne,l5
cycloptadiene,16 morpholine, 17 and methylene,l 8 and octahedral dispositions of
these groups, though not yet confirmed, is highly probable. Octahedral addition is also
produced by two identical trios of (mutually orthogonal) additions, whereby the first trio
conserves the decacyclene moiety which is a common feature of a number of stable
Illerenes. 13
4
The smaller of these groups may also add at fixther sites in the molecule, and
evidence that for this is provided by the formation of epoxides derived fiom
fluorornerenes, with up to eighteen oxygens attached to the cage . l9
(a) (b)
Ngure 4 Products that can in principle arise from reaction of a group X at a 6:6-dngjunction
(4 (b)
Ngure 5 Products that can in principle arise from reactionof a group X at a 5:6-ringJunction
5
Addition of such groups e.g. CH2 commonly takes place across a 1,2-bond (6:6-
ring junction) to give a bridged (methanofuUerene) structure (Fig 4a), rather than an
inserted one (homofkUerene or fulleroid, Fig. 4b) because the former maintains the
favourablearrangement of double bonds being exocyclic to ~entagons.2072~ Conversely
however, insertion into the lp-bond (5:6-ringjunction) is favoured (Fig 5a) because this
not only gives the preferred benzenoid structure in one of the hexagons, but the
alternativebridged structure(Fig. 5b) would have a double bond in a pentagon.2*>21
1.2. Gtoups with Small &lipsing inteructiom-AaZition of Hydrogen.Hydrogen adds
across the 1,2-bond in [6O]fullerene and the 1,2- and 5,6-bonds in [70]fi~llerene(new
numbering - see Fig. 8), to &ve the corresponding dihydrolllerenes. Further addition
can then take place across the equivalent bonds throughout the molecule, giving first a
variety of tetrahydro derivatives (see Chapter 4), and then higher hydrogenated
derivatives.22Although the low steric interactions suggest that in principle it should be
possible to produce the filly hydrogenated derivatives, evidence for these has not yet
been obtained, possibly because all of the C-Hbonds will be eclipsed, and the eclipsing
can be relieved only slightly by twisting of the C-C bonds of the cage. Moreover,
addition tends to stop at C6$36 (see Chap. 4), this compound being particularly stable
because the T isomer (Fig. 4) contains four benzenoid rings;13720323 further addition to
these highly delocalised rings is then difficult. It is also significant that octahedral
addition is on the pathway to the Tisomer of C6$36.
Figure 6 Schlegel diagram for the T isomer of C60H-36; (l3) denotes benzenoid rings.
6
Addition to [7O]fullerene also stops largely at the C70H36 stage, though here,
significant amounts of C7oH3g and C7OH40 are also produced.24 This can be explained
by the formation of an equatorialbelt of either two phenanthrenoid Mgs and a bewenoid
one @is. 7) or of one phenanthrenoid ring and two naphthalenoid ones.25 Further
reduction of the bonds corresponding to the 9,lO-bonds in phenanthrene (encirded in
Fig. 7) accounts for the two higher reduction levels obtained. These structures may in
due course be found to have importance in other additions of [7O]lllerene.
Figare 7 Schiegel diagram for a proposed structure of C70H36; aromatic regions outlined,and
9,IO-bondof phenanthrene moiety encircled
1.3. Groups with Moderate Eclipsing Interactions. Fluorine falls into this category, and
there is general agreement amongst the various reports that ca forty-eight fluorines can
be added without much difficulty (Chap. 6). Thereafter it becomes progressively harder
to add the remaining twelve fluorines to produce the hlly saturated derivative but has
been achieved. The question as to why fluorination does not stop at the thirty-six
hydrogen stage, as hydrogenation laregly does, can be attributabed to the much lower
activation energy for fluorination compared to hydrogenation.
1.4. Groups with h r g e Steric Znteractions. The situation here awaits further
clarification. Radicals formed by the addition of R groups to (6O]fhllerene adopt a
structure such that the groups are beta to a pentagonal ring, this having the advantages
7
that the groups do not steridy interact and the radical is delocalised around the
p e n t q p d ring (Chap. 13).25 It should also be possible to produce a diradid with each
radical delocalisad around diametrically opposed pentagons. There are also five other
(equivalent) pentagonal rings that could be the centm for radical addition, but such
additioa would introduce a measure of steric interactionwhich is probably unfavourable.
Up to twenty-four chlorine or bromine atoms can be added to [6O]fIdlerene, and
in the redant derivativeno two addends are adjacent to each other, which follows &om
the e x p t e d stcric interactions. In the C6& compounds, (the structures of which
r e w n b h that for the radicals) one pair of halogens are adjacent, and this is true also for
C70Cl10 (we Chap. 7), but this is probably as much eclipsing that can be tolerated. As in
the case of the radicals one further pentagon could be a probable centre for addition, so
that compsund C6oX12 should be isolable. In the compound C60Br8 the bromines are
also nolladjacent, and in principle it should be possible to produce C M r 1 6 with the
same sieht-fold disposition ofthe bromine atoms, but this derivativewould not be on the
pathway to CMr24; C&rZo with benzenoid rings at opposite poles also seems a
feasiblederivative.
The bulkiest groups that have been attached to the [6O]fullerene are
pertluodkyls and phenyl (Chaps. 13 and 8), with evidence for the addition of up to 16
groups, though the locations are unknown as yet.26
In summary a correlation is emerging between the sue of the addend and the
number that can be attached to the cage. In due course one can expect to see a further
correlation between the number of addends for a particular reaction, and the size of the
tiJllerem.
2. Numbering of Fullereneta
In this section the hllerene numbering schemes that seem likely to be
recommended by IUPAC are presented in the form of Schlegel diagrams. To obtain
these dhgams, one pole of the fullerene is expanded whilst the other one is shrunk until
a t w d i s i o n a l representationis obtained.
There is no doubt that the speed with which chemists began to make derivatives
of fidhnes caught nomenclaturists unawares. Consequently a numbering system for
[6O]lllsrene involving numbering around a pentagon was provisionally intr0duced,2~
and seemed logical enough since there is a similar pentagonal cap in [70]lllerene.
However, it transpired that contiguous numbering cannot be achieved in [70]fillereneby
numbating from the pentagonal cap (Fig. 8), and moreover it quickly became clear that
8
one bond in [6O]fullerene is the site of nearly all reactions. It made sense therefore to
number this as the 1,2-bond, and hence to commence numbering around a hexagon (Fig.
9).28 Further consideration has revealed that contiguous numbering can be achieved in
[7O]lUerene by numbering around a hexagon adjacent to the pentagonal cap (Fig. lo),
and this has the advantage that the most reactive bond in [70]fhllerene is also the 1,2-
bond, and carbons 1-38 have the same environments in both molecules. The system given
by Figure 8 has been used in a number of papers hitherto, and in some parts of this book.
However, it is recommended that henceforth the more convenient system given in Figure
10 should be used.
Before giving examples of the numbering schemes it is necessary to elaborate
fhrther on the description of the fhllerene. For [60]fullerene and [70]fullerene only two
isomers concern us (at least in relation to the chemistry), and so it is unnecessary to give
the fid descriptions viz. [60-Zh]fullerene and [70-D5h]fullerene respectively. Where, due
to degeneracy, subdivision is necessary, then this is indicated by capital Roman numerals.
These are assigned priority on the basis of the lowest numeral sequence at the first point
of difference, when the incidence of the 12 pentagonal faces in a ring spiral is stated as a
list of numbers in the range 1 to n/2 + 2 in ascending order, using the sequence given in
the 'Atlas of Fullerenes' by P.W. Fowler and D. E. Manolopoulos, O.U. Press, 1994.
These degeneracies have been indicated previously by various other methods some of
which have been directly contradictory. Henceforth, only the designations given in
Figures 11-22, which show some isolated pentagon isomers of [76-, 78-, 82-, and
84]fidlerenes, should be used. Not all of these fdlerenes have yet been isolated and
characterised
9
58
"" OY
I5
ie
13
79
8*
The term hlleroids has been used provisionally to describe some carbon-bridged
derivatives of [6O]hllerenes, but these can now be replaced by the existing organic
nomenclature, as exemplified in Figures 23 and 24.
The tam endohedrai which has been introduced to describe fbllerenes with entities
inside the cage is as yet not a problem since no derivatives of them have been made.
However,inevitably this situation will change, and conflict will arise with Diels-Alder
adducts possessing endo and em substituentson the addend. To forestall this problem it
is recommended by IUPAC that since the term incurceranes already exists as an
approved nomenclature term, the term incur (symbol i) be used henceforth to describe
non-empty Illerenes.
Lastly, though strictly not nomenclature, the notations for the carbon atoms in
Fig. 25 has been fbund useful by many workers
e d c b a
Figure 25. Notation for the five different types of carbon atoms in [7O]futlerene
18
References
FuUerene Production
LowellD. Lamb
Department of Physics, University of Arizona, Tucson, Arizona 85721, USA
1 Introduction
Fullerene production is a simple process (see Figure 1). A large electric current is
paased through graphite rods in a quenching atmosphere of inert gas, thus evaporating
the rods to produce a light, fluffy condensate called fullerene soot. Under the right
conditions a substantial fraction is comprised of fullerenes, and they can be extracted
either by sublimation or, more commonly, by solvation. In spite of the use of the
term soot, this is not a combustion product; pure carbon is vaporized in aa inert
atmosphere, and the vapor condenses into a variety of forms including the fullerenes.
Besides Ceo and C70, hundreds of larger fullerenes, endohedral fullerenes, single- and
multi-walled nanotubes and nanoparticles, and nanotubes and nanoparticles contain-
ing nanocrystals of foreign materials can be made simply and in abundance. This
chapter will give an overview of the Kratschmer-Huffman process [2] and its variants,
with special emphasis on the practical aspects of obtaining Cm and CT0.Concerning
the published literature, an attempt will be made to cite recent and comprehensive
articles instead of trying to give a complete history of production.
2 Soot Production
The fullerene-soot generators currently in use can be divided into two broad
classes: small bench-top chambers intended for the production of limited quan-
tities of soot (on the order of 10-20 grams per day) and large, high-output chambers
capable of producing hundreds of grams of soot per day. A small chamber, if adequate,
offers a number of advantages including simplicity and low cost. Good descriptions
of bench-top soot chambers have been published by Koch et al. [3] and by Scrivens
and Tour [4]. In both cases the reaction vessel was made from commercially available
glassware, out-of-pocket expenses were several hundred dollars, and construction re-
quired a few hours of machine work and a few days of labor. If a large soot generator
is needed, there are several issues that have added importance in the design. These
include turn-around time (i.e., the time between burns required to cool the cham-
ber, break vacuum, install a new rod (or rods), and to pump and purge the system),
the amount of soot generated per burn (i.e., the rod diameter and the maximum
length of rod that can be burned), soot harvesting, and, probably most important,
the generation of large amounts of heat. To deal with the last problem virtually all of
20
21
I to-
&%%!!
a-
Figure 1: Basic steps in fullerene production [l].
the large chambers are water cooled in some way. For example, in various fullerene-
soot generators at the University of Arizona both electrodes are water-cooled and a
water-cooled shroud shields the chamber from direct radiation from the arc. Good
discussions of large chambers (with drawings) can be found in articles by Haufler et
al. [5] and Parker et al. IS]. Excluding the vacuum pump and power supply (which
may be larger and more expensive than those needed for a small chamber), the con-
version of an existing vacuum chamber into a large fullerene-soot generator may cost
$1,000-2,000 and require several weeks of labor.
The optimum conditions for soot production are extremely chamber- and technique-
dependent. Indeed, all of the influential variables in the process probably have not
been identified, let alone had their effects characterized. Variables that appear to
be universally important include quenching-gas species and purity, chamber pressure,
and rod size. Variables whose importance is less clearly understood, or that seem to
be more important in some chambers than in others, include voltage, current,.burn
rate, the use of an ax. versus a d.c. power supply, chamber dimensions and geometry
(including the presence of cooled collection-surfaces),type of burn, static versus flow-
through quenching atmosphere, convection, and the effects of arc-produced radiation
on the soot. Brief discussions of some of these variables follow.
Although fullerenes will form in a variety of inert atmospheres (e. g., argon and
moleculaz nitrogen 1511, a t present helium is the universal choice because the yields
are substantially higher [5],[7].In this context the yield is the fraction of the soot that
22
3 Extraction
.Although the fullerenes axe soluble in a wide variety of suhents [la], toluene is
most commonly used because of its low cost, relative safety, low boiling point, and
24
reasonably large capacity for carrying fullerenes in solution (at room temperature,
saturation of C a in toluene occurs at z2.8 mg/ml [14]). As a usual first step, mixed
fullerenes (typically consisting of ~ 8 0 % C ~ O%20%
, Cto, and 31% larger fullerenes)
are extracted from the soot with toluene, either in a Soxhlet apparatus or simply by
dispersing the soot in tofuene and filtering (cold extraction). In a cold extraction it
may be helpful to sonicate the soot/tohene slurry before filtering. Depending upon
the soot/solvent ratio of the initial wash, it may be useful to repeat the procedure
more than once. At the University of Arizona excellent results have been obtained
by: (1) adding 40 grams of fullerene soot to 4 liters of toluene in a glass bottle
and vigorously shaking the bottle to mix thoroughly; (2) leaving the bottle to stand
overnight, thus allowing the vast majority of the insoluble component of the soot to
settle; (3) carefully decanting the reddish-brown liquor from the bottle, disturbing
the undissolved soot as little as possible; (4) filtering the liquor with a coarse and
then a fine paper filter. Because a substantial fraction of fullerene soot is composed of
graphitic particles 0.1 pm or less in diameter, considerable care must be taken in this
step to insure that all particulate matter indeed is removed from the liquor. Using a
short chromatography column as a find filtration step may be more effective than a
paper filter [8],I15j; ( 5 ) removing the toluene with a rotary evaporator, leaving the
mixed fullerenes in the form of a crystalline powder (extract); and (6) collecting
the depleted fullerene soot from several first washes and repeating steps (1)-(5)2 or
3 times, depending upon the color of the third wash.
The wide range in reported typical yields of extract (=6-20%) almost certainly
is due in part to the lack of a standardized assaying method. Besides the most
common methods of mass balancing and HPLC (an HPLC protocol described in a
paper by Diederich and Whetten [16] has been used with excellent results at the
University of Arizona), mass spectrometry and uv-visible absorption spectroacopy
have also been used. It is not likely, however, that differences in analytical methods
constitute the entire explanation for the large variation in the reported yields. One
important possibility is contamination. Any soluble contaminants origindly present
in the soot (PAHs, vacuum grease, pump oil, etc.) will be in the extract, and they
should be removed before the final yield determination. At the University of Arizona
contaminants are routinely removed by first thoroughly washing the extract with
hexane or ether and then gently baking the sample under vacuum.
4 Separation
2-3 days and large quantities of c70 in 7-10 days. More recently, several activated-
charcoal-based systems for the purification of Cm and C70 have been described 1181-
1211. This approach is especially well suited for preparation of c60; with the proper
choice of activated charcoal several grams of very pure Cm may be obtained in =30
minutes via straightforward plug-filtration of fullerene/toluene solutions 1191, [21].
High-purity C70 also may be obtained using either flash chromatography 1201 or the
recycling apparatus used for the hexanelalumina system [Zl]. Although flash chro-
matography is faster (a few hours versus 2 days for the recycling system), it should
be noted that for each gram of pure c70 prepared in this fashion ~ 1 liters
0 of 1,2-
dichlorobenzene (boiling point: 178 C) must be removed with a rotary evaporator.
It is now well known that fullerene soot contains hundreds of larger, soluble, all-
carbon clusters besides C ~ and
O (270. Fullerenes as large as have been detected
with mass spectrometry in solvent extracts [22], and it appears that in these mix-
tures of larger fullerenes every even-numbered carbon cluster beyond Css is present
in some concentration. In addition to the large, even-numberedclusters present in
the soot several stable, toluene-soluble, odd-numbered clusters (C,,,, C ~ Z Band
, C139)
have been found [23].Using high-boiling-pointsolvents such as l12,4-trichlorobenzene
appreciable quantities of mixed, larger fullerenes can be extracted from depleted
fullerene soot (i.e., soot that first has been washed thoroughly with toluene to re-
move as much C ~ andO c70 as possible) [13]. Excellent discussionsof various extraction
schemes can be found in papers by Parker et al. [6], [24], by Smart et af. [25], and by
Diederich and Whetten [l6]. Of this extensive family of molecules only a few of the
smaller, even-numbered species have been isolated. After Cm and (270, the next most
abundant species are c76, C78, and C S ~and , tens of milligrams of these molecules
have been isolated using normal column chromatography and HPLC [13], [16], [26],
[27]. Beyond these, however, the problems of separation are formidable [26]-[28].
5 Endohedral Fullerenes
The doped rods used in endohedral production typically are prepared by: (1)
boring a coaxial hole in a graphite rod; (2) packing the resulting cavity with a mixture
of graphite cement and metal powder, metal oxide, or metal carbide, with the metal
content being a few percent of the overall carbon content; and (3) baking the rod
in a vacuum or inert atmosphere to graphitize the cement and drive off any volatile
species. The total and relative yields of the metallofullerenes can vary considerably
with the level of doping. In general, a smaller metal fraction results in a higher
overall yield of metallofullerenes with single-metal-atom species dominating, and a
higher metal fraction results in a lower overall yield with multiple-metal-atom species
dominating [32]. Although endohedral fullerena can be synthesized with reasonable
yields using such rods, they always occur together with a mixture of empty fullerenes,
and isolating even small amounts of individual endohedral species requires multi-step
HPLC protocols [33], [34]. Greatly complicating the problem is the fact that many
endohedral species are air sensitive; for example, LaQCal is quite stable and has
been extracted, isolated, and characterized without special handling [34], while the
extraction of LaQC76 has been possible only under anaerobic conditions [35]. Bethune
et al. have recently reported the isolation of milligram quantities of SczQC8.l and tmme
characterization of its crystalline phase [32].
Using high pressure and temperature, Saunders et al. have recently produced
macroscopic quantities of MQC60 and MQC70, with M = He, Ne, Ar, Kr, or Xe
[36]. By heating a solid c60/c70 mixture at a temperature of ~ 6 0 0 C for several
hours in the presence of a noble gas with a pressure in the 20,000-40,000 psi range,
they obtained yields as high as a few tenths of a percent of the endohedral product
relative to the empty fullerene precursor. These extraordinary materials are soluble
in toluene and apparently include the first stable compounds involving helium and
neon. Sufficiently large samples of 3HeQCm and 3HeQC,0 have been made to allow
NMR characterization [37].
6 N a n o t u b e s a n d Nanoparticles
In addition to the fullerenes and endohedral fullerenes, we now know that other
classes of carbon-based materials can be produced by vaporizing graphite (or doped
graphite) in an appropriate atmosphere, namely carbon nanotubes (buckytubes)
and nanoparticles. These fascinating structures can be synthesized in gram quantities,
and it has been speculated that applications may include electronics, magnetic storage
of information, gas storage, catalysis, chemical separation, and composite materials.
Below are brief discussions of the production and separation methods now in we.
Following Iijimas initial report [38] of finding carbon nanotubes in a deposit on
the cathode of a fullerene-soot generator, Ebbesen & Ajayan published a recipe for
making large quantities of this novel class of carbon structures [39]. Using a typical
fullerene-production apparatus and a higher pressure than normal (500 Torr instead
27
of the usual 100-200 Torr), they found conditions under which a particular type of
carbonaceous deposit would form on the cathode. In electron-microscopy studies
of these Structures it waa discovered that certain interior regions contained copious
quantitiee of carbon nanotubes mixed with carbon nanoparticles. Tubes that are pro-
duced in this fashion typically consist of two or more concentric shells, with diameters
ranging from 2 to 20 nanometers and lengths sometimes as great as several microm-
eters. The nanoparticles are typically tens of nanometers in diameter, and consist
of many concentric graphitic layers. Systematic studies of the effects of varying the
production parameters on the yield and morphology of the nanotubes have been pub-
lished by Ando and Iijima [40] and Seraphin et al. [41], and an overview of the field
may be found in a review article by Ebbesen [42]. It is worth noting that although
fullerenes, nanotubes and nanoparticles can form in the same environment, and that
their formation processes are clearly related, nanotubes and nanoparticles form in
significant yield under a broader range of conditions than do fullerenes. For example,
it is possible to make nanotubes and nanoparticles, but not fullerenes, in a quenching
atmosphere of CHI [40]. Although the tangled mixture of nanotubes and nanoparti-
clea has not (to the authors knowledge) proved separable via any standard technique,
Ebbeatn and coworkers have reported the isolation of pure nanotubes by heating mix-
tures of nanotubes and nanoparticlee in pure oxygen [43]. The nanoparticles burn
more quickly than do the nanotubes, and although ~ 9 9 % of the starting material is
consumed in the process a sample composed solely of nanotubes is obtained.
Making up a separate claas of fullerene-related structures are the single-walled
buckytubes, which can be made copiously under the right conditions [44]. In this
p r o m the presence of a transition metal (Fe, Co, Ni) as a catalyst is an important
requirement. Unlike the multi-walled tubes, these tubes are not found in the cathode
deposit. Rather, they are mixed with carbon nanoparticles in web-like structures
and rubbery sheets in the soot, and are made easily in gram quantities. The small
diameters of these tubes (-1 nm) and their location in the soot suggests that the
single-walled tubes are closer relatives of the fullerenes than are the multi-walled
tubes and particles discussed above. The yields, lengths, and distribution of radii of
the tubes are greatly affected by the choice of catalyst and other parameters [45].
The covaporiaation of metals and carbon has been exploited by various groups
with two objectives: to influence the yields and morphologies of pure-carbon nan-
otubea and nanocrystals, and to produce nanocrystals of various compounds that
are completely within nested carbon structures. By doping the electrodes with met-
als, carbides, or metal oxides (in the same manner as for the production of endohe-
dral fullerenes) and by properly choosing the production conditions, nanotubes and
nanoparticles have been formed that encapsulate nanocrystals containing Y, La, Ce
Pr, Nd,Gd, Tb, Dy, Ho, Er, Lu, Co, Fe, or Ni. An excellent overview of the field may
be found in an article by Saito et al. [46]. Particularly interesting has been the obser-
vation by the Carnegie Mellon University group (Pittsburgh, Pennsylvania USA) of
28
The fullerene production techniques involving the laser ablation of graphite [29],
sputtering or electron-beam evaporation of graphite [48], inductive heating of graphite
[49], vaporization of graphite powder in an Ar plasma jet [50], and the use of con-
centrated solar radiation to vaporize graphite [9], [51], appear to be close relatives
of the original Kratschmer-Huffman method [2]. In all cases pure graphite is va-
porized in the presence of an inert, quenching atmosphere, and the resulting vapor
condenses into a fullerene-bearing soot. It is not unreasonable to speculate that the
fullerene-formation mechanisms for these processes are very similar. However, it is not
clear what the relationships are among evaporative fullerene formation, formation
of fullerenes in a special class of sooting flames [52], and formation of fullerenes via
pyrolysis of naphthalene 153). In the first of these non-evaporative processes, special,
subatmospheric-pressure benzene/oxygen flames have readily produced gram quanti-
ties of soot with 20% fullerene yields. Besides possessing the potentially important
advantage of being an exothermic reaction, it is possible to tune the Cm/Cm ra-
tio over a wide range by adjusting the flame conditions. An excellent review of this
method is found in an article by Howard et al. (541. In the other non-evaporative
technique, Taylor et al. have shown that pyrolytic decomposition of naphthalene in a
low-temperature (1000 C) argon atmosphere can result in the formation of macro-
scopic quantities of c60 and C,O via combination of Clo fragments [53]. As they point
out, this process in principle could be operated in a continuous fashion, and it may
prove possible to form selectively a particular fullerene or even endohedral fullerene
by choosing judiciously the hydrocarbon precursor and other reactants.
The major problems with the chromatographic techniques discussed in Section 4
are stated easily: besides c60 and C70, only a few of the hundreds of other fullerenes
and endohedral fullerenes can be isolated in any quantity, and then only with an
enormous investment of effort and other resources; a significant quantity of the start-
ing material is lost irretrievably with any of the methods currently in use; and the
final product invariably contains trace amounts of solvent trapped in the solid, Of
the other approaches that have been tried because of these difficulties, a few deserve
brief mention. Darwish et al. report that the careful concentration of an already
saturated C60/C70 solution results in the precipitation of a solid that is richer in C70
29
than the starting solution, and by repeating the process several times high-purity C70
may b obtained [21]. As they point out, this method is suitable for large scale pro-
cesaing, and there are no ~ O S W with repeated cycling. In a similar vein, Ruoff et al.
have made progress in enriching the higher-fullerenecontent of fullerene mixtures us-
ing selective-extraction techniques [55]. Another widely discussed approach involves
chemical modification of the fullerenes to facilitate separation. For example, Atwood
et at. [as] and Suzuki et al. 1571 have reported the purification of Cm and c70 by
reversible complexation with calixarenes, which are bowl-shaped molecules that se-
lectively bind to Cm in a toluene solution. Briefly, the calixarene/Cso complex forms
a precipitate in toluene that is filtered out and redissolved in chloroform, whereupon
the complex decomposes and the Cm forms a precipitate while the calixarene stays
in solution. Although it is not clear that this approach is superior to the activated-
charcoal-based schemes for the large-scale preparation of CSOand C T ~the , idea of
someday being able to design a complexation 'partner" for a specific fullerene or en-
dohedral fullerene is very appealing, given the current unsatisfactory state of the art.
Lastly, the convenience and effectiveness of solvent-based extraction and separation
are not without price; residual amounts of the solvent invariably are trapped in the
interstices of any fullerene crystal that has been grown out of solution. Prolonged
baking under vacuum does not remove fully this stubborn form of contamination, and
sublimation or even repeated sublimation in a vacuum may be the only certain way
of purifying completely fullerenes that have been in solution. Accordingly, there has
been some work on the extraction and Separation of the fullerenes via sublimation
and trmsport in an inert gas [58]. The total fullerene yields can be comparable to
those obtained by toluene extraction, and high-purity Cm and C70 samples have been
made.
Soot-making: When using a glass reaction vessel, thought must be given to the
heating of the glass during soot production, as heat-induced stress may lead to im-
plosive failure. If the arc is monitored visually, appropriate, uv-blocking eye-protection
should be used. It is important to note that not all dark glasses offer sufficient uv-
30
protection, and the use of uv-transparent dark glasses may actually increase the risk
of eye damage, as the eye will dilate in response to the attenuation of the visible
output of the arc. As discussed above, impurities in the rods, quenching gas, or those
present due to chamber leaks should be minimized to reduce the chances of forming
PAHs.
Soot harvesting a n d handling: There is a very strong sentiment in the fullerene
community that inadvertent, long-term inhalation of airborne fullerene-soot particles
is the most serious potential health problem commonly encountered in fullerene pro-
duction, Once these particles are airborne they are very difficult to filter out of the air,
and the use of adequate hoods with high air-flow rates is strongly recommended, It is
well known that inhaling of any type of particulate contamination over an extended
period can result in serious lung damage. Given that very little is known about the
health impact of exposure to fullerene soot, and that it is common for diseases caused
by inhalation of particles to take years to develop, there is a very real and compelling
need to prevent inhalation of and skin contact with the soot.
Solvents: All of the solvents commonly used in fullerene production are toxic, in-
flammable or explosive, and many are carcinogenic, mutagenic, or teratogenic. When
using these chemicals standard laboratory procedures should be carefully followed.
All solvents should be safely stored, gloves should be worn to avoid skin contact,
open containers of solvent should be handled only in well-ventilated hoods, and used
solvents should be disposed of properly.
H e a v y metals: Many of the materials used in endohedral-fullerene production are
known toxins (e. g., heavy metals), and should be handled using standard laboratory
procedures.
Fullerene-containing materials: Although there has been no indication to date
that the most common fullerenes and fullerene-containing materials ( C ~ OC, ~ Oetc.)
,
are dangerous in any way, until the actual health impact has been determined pru-
dence dictates that these substances be treated with the same respect accorded any
other unknown chemical. Specifically, care should be taken to prevent ingestion,
inhalation, or contact with the skin.
Acknowledgments
The author thanks M. C. Zumwalt for assistance in preparing the figure, and
also thanks the Division of Advanced Energy Projects of the Office of Basic Energy
Sciences, Department on Energy for kind support of this work.
31
References
[l] Figure adapted from D. R. Huffman, Physics Today 44, no. 11 (1991) 22-29.
[2] W. Krjitschmer, L. D. Lamb, K. Fostiropoulos, and D. R. Huffman, Nature 347
(1990) 354-358.
[3] A. S. Koch, K.C. Khemani, and F. Wudl, J. Org. Chem. 56 (1991) 4543-4545.
[4] W. A. Scrivens and J. M. Tour, J . Org. Chem. 57 (1992) 6932-6936.
[5] R. E. Haufler, Y. Chai, L. P. F. Chibante, J. Conceicao, C. Jin, L.-S. Wang, S.
Maruyama, and R. E. Smalley, Mat. Res. SOC.Syrnp. Proc. 208 (1991) 627-637.
[6] D. H. Parker, K. Chatterjee, P. Wurz, K. R. Lykke, M. J. Pellin, L. M. Stock,
and J. C. Hemminger, Carbon 30 (1992) 1167-1182.
[7] Y. Saito, M. Inagaki, H. Shinohara, H. Nagashima, M. Ohkohchi, and Y. Ando,
Chem. Phys. Lett. 200 (1992) 643-648.
(181 W. A. Scrivens, P. V. Bedworth, and J. M. Tour, J. Am. Chem. Soc. 114 (1992)
7917-79 19.
I191 L. Isaccs, A. Wehrsig, and F. Diederich, Helu. Chim. Acta 76 (1993) 1231-1250.
[20] W. A. Scrivens, A. M. Cassell, B. North, and J. M. Tour, J. Am. Chem. SOC.,
Communication, in press (1994).
(21) A. D. Darwish, H. W. Kroto, R. Taylor, and D. R. M. Walton, J . Chem. SOC.,
Chem. Commun. 1994,15-16.
[22] H.Shinohara, H. Sato, Y. Saito, A. Izuoka, T. Sugawara, H. Ito, T. Sakurai, and
T. Matsuo, Rapid Comm. Mass. Spec. 6 (1992) 413-416.
[23] S. W. McElvany, J. H. Callahan, M. M. Ross, L. D. Lamb, and D. R. Huffman,
Science 260 (1993) 1632-1634.
[24] I). H. Parker, P. Wurz, K. Chatterjee, K. R. Lykke, J. E. Hunt, M. J. Pellin, J.
C . Hemminger, D. M. Gruen, and L. M. Stock, J. Am. Chem. SOC.113 (1991)
7499-7503.
[25] C . Smart, B. Eldrige, W. Reuter, J. A. Zimmerman, W. R. Creasy, N. Rivera,
and R. S. Ruoff, Chem. Phys. Lett. 188 (1992) 171-176.
I261 K. Kikuchi, N. Nakahara, M. Honda, S; Suzuki, K. Saito, H. Shiromaru, K. Ya-
mauchi, I. Ikemoto, T. Kuramochi, S. Hino, and Y. Achiba, Chem. Lett. (Japan)
1991 1607-1610; K. Kikuchi, N. Nakahara, T. Wakabayashi, M. Honda, H. Mat-
sumiya, T. Moriwaki, s. Suzuki, H. Shiromaru, K. Saito, K. Yamauchi, I. Ike-
moto, and Y . Achiba, Chem. Phys. Lett. 188 (1992) 177-180.
[27] R. Taylor, C. J. Langley, A. G. Avent, T. J. S. Dennis, H. W. Kroto, and D. R.
M. Walton, J . Chem. Soc., Perkin Trans. 2 1993,1029-1036.
[28] Y . Achiba, K. Kikuchi, T. Wakabayashi, N. Nakahara, and S. Suzuki, Higher
Fullerenes: Isolation, Characterization, and Growth Mechanisms, in Proceedings
of the First Italian Workshop on Fullerenes: Status and Perspectives, Bologna,
6,7February, 1992,C. Taliani, G. Ruani, and R. Zamboni, Eds. (World Scientific,
Singapore, 1992) 13-19.
[291 Y . Chai, T. Guo, C. Jin, R. E. Haufler, L. P. F. Chibante, J. Fure, L. Wang, J.
M. Alford, and R. E. Smalley, J. Phys. Chem. 95 (1991) 7564-7568.
33
Properties of Fullerenes
Roger Taylor
Investigationof the physical properties of lllerenes has been most intensive, and
has r d t e i in the pubfiation of many thousands of papers. However, much of the
published information is of less direct interest to the synthetic chemist, and only the most
salient htures are considered in this chapter. For practical purposes, description is
limited to [60]-, [70]-, [76]-, [78]-, [82]-, and [84]lllerenes. Given that [76-
84]Mermes comprise only about 1% of the soot extract, and isolation of 1 mg of the
pure mmpounds is hugely expensive in both time (ca.250 h are required) and solvents,
and requires state-of-theart High Pressure Liquid Chromatography, it is not surprising
therefire that to date, little or no chemistry has been performed on these compounds.
For even higher fillerenes the problem becomes an order of magnitude more difficult,
and bianing some technological breakthrough, the chemistry of these is untikely to
concern us during the next decade. Even when significant amounts of these componds
becomcr available, there will be difficulties due to the decreasing solubility and reactivity
that p d d s increasing molecular weight of fkllerenes
35
36
The extinction coefficient of [70]firllerene in the visible is higher than that for
[6O]Olfullerene. A consequence is that mere traces of the former in solutions of the latter
impart a d o u r detectable to the eye. This enables experienced workers to judge the
purity of chromatographically purified samples of [6O]fbllerene without recourse to time-
consuming 13C NMR analysis. Unfortunately the reverse is not the case and solutions of
[70]fUllerene containing as much as 70% of [60]hllerene are visibly indistinguishable
from pure [70]hUerene. This led to some embarassment by fledgling lllerene
manufacturers who lacked (as is usually the case) the necessary analytical equipment.
[6O]Fullerene is the material that most workers wilI become familiar with.
Although it is black in the solid, very finely divided material can appear brown. However,
material in the latter form is preferably to be avoided since the tendency towards
atmospheric oxidation increases with surface area. Crystals of various shapes and S i z e s
can be grown easily e.g. from benzene, needles appear which are actuaUy a series of
overlapping plates rather like a cart spring.1 If however the recrystallisation fiom
benzene is very slow, deep magenta crystals of [SO]&llerene.4C& are obtained.6 Most
material is supplied fiom manufacturers as granules ranging in size up to cu. 1 mm3,
Unless suppliers have been meticulous in removing occluded solvents (and dioctyl
phthdate, the plasticiser present in all solvents including those claimed to be of HPLC
grade), and even ~ulphur,~ it will be necessary for rigorous work to sublime the fbllerene
in vacuum (at cu. 400 "C and 0.01 W g ) . In this way, ciystds in excess of 100 mg in
weight have been grown.
For preparative chemistry (as opposed to physical measurements) it will in most
cases be unnecessary to purifjr by sublimation. The purification regime devised by the
writer consists of removal of solvent after chromatographic separation (this is most
Simply, rapidly, and economically carried out using a column packed with Norit 'Elorit'
grade carbon).8 The resultant solid is then digested repeatedly with AR grade acetone
until the supernatant liquid (removed each time with a Pasteur pipette becomes
colourless (this removes non-fullerene impurities), and after removal of residual acetone
(under nitrogen), heating the solid at cu. 170 *C at 0 5 mmHg for 2 h.8 Because the
crystal packing improves with increasing purity, pure [60]fullerene is significantly harder
to dissolve than less pure material. The same purification regime and solubility aspects
apply to [7O]hllerene.
The next problem to be faced is the determination of the purity of the material
that is available. This is difficult, and little notice should be taken of early papers claiming
quite unmeasurable purities, and not too much should be taken of some manufacturers
37
claims. For example, purity said to be 'checked by HPLC' can be misleading unless great
carc hu been taken to compensate for the differences in extinction coefficients of the
other W m n e 'impurities'. This is particularly true of [70]fillerene because the lower
extiuchn wefiicient of [6O]fullerene, the usual impurity, means that estimates of its
mnCdlltration may be too low. There are problems too with mass spectrometry, because
the voktility of lllerenes decreases markedly with increasing cage size, and unless the
temperakrre of the probe is ramped quickly up to that at which the ions appear for the
higher fbllerenes, they may appear to be absent; their concentrationswill not in any case
be proportional to the ion intensities.
1.1 13CN M R Spctrosco~.The most reliable indicator of purity is 1% but here
there are difidties because of the differing numbers of identical carbons in a given
fUma~e.Thus for example, [7O]hllerene, having five carbon types gives ca.one-fifth of
the si@ intensity for each carbon atom compared to [6O]fillerene. Thus the presence of
[70]iUame in [6O]fullerene can go undetected unless a sufficiently long accumulation
time for the spectrum is used. The problem is of course exacerbated with the higher (and
less symmetrical) hllerenes. The shorten the accumulation time, chromium (acac)3 is
usually employed as a relaxation agent, and provided the relaxation times are sufficiently
long (a total of 6 s for relaxation plus acquisition is adequate), each hllerene will give
signals proportional to their concentrations. The chromium compound can be removed
and the pure fullerene recovered, by repeated digestion with acetone (in which the
hllercne is insoluble), and removal of the Supernatant liquid by means of a Pasteur
pipette. The chemical shifts obtained will depend slightly on the solvent used for
obtainiag the spectrum, and also on the deuteriated compound used for the lock signal.
Figures 1-3 show 13C N M R spectra for [60-Ih]-,14 [70-Lk,h]-,14 and [76-
02]Werenes.2 Figure 4 shows the spectrum for the C2v(I) isomer of [78]fUllerene,S
Figures 5 and 6 are the spectra for mixtures (differing proportions) of the C2V(I)-,
CzV@)-, and D3-isomers of [78]111erene~;~31~ lines for [76]fUllerene and traces of [60]-
and [70]fullerenes10 have been deleted for clarity in Figure 6. The proportions of the
various [78]hllerene isomers obtained are very dependent upon reactor conditions.1
Figure 7 shows the spectrum for a mixture of C2-, QV, and C3,,-isomers of
[82]flrlleiene? and Figure 8 shows two spectra for a mixture of the Dz(1V)- and &&I)
isomers of [84]f~lIerene;~~10 the latter shows how reproducible the spectra can be,
provided that the stabilities of the component isomers are similar, and are thus produced
in comparable quantitiesin different reactors.12
38
I
- - w
1 1 1 1 1 1 1 ~ 1 1 1 ~ 1 * ~ 1
F i p m 5 (above) and 6 I3C NMR spectra in CS2 for mixtures (Merent proposrtions)of
[78]fullerene isomers (starred lines in Fig. 6 are half-intensity)
II .
. . I I
Figure 8 13C NMR spectra for a mixure of D2 and D2d isomers of [84]fullerenes
41
535.5, 565.7, 578.0, 642.4, 674.2, 795.1, 1087.0, 1133.2, 1414.0, 1430.7, and 1461.0
cm-1.13 Before running IR spectra, it is important that the fullerene should be baked as
described above, otherwisebands due to occluded solvent will appear. Even thin films of
fhUerene, deposited from solvents onto KBr plates, required prolonged heating under
vacuum at 200 "C before traces of solvent are completely removed.
No IR spectra have yet been published for higher fullerenes.
1.3. Raman Spcfroscopy. Raman spectroscopy is another means of charactmising
[a]-
and [70]fullerenes, though the equipment needed for accurate work (1 cm-1
resolution) is not widely available. Spectra have been obtained for both Mlerenes p i p r e
10% b)16 (6also ref 17). The vibrational frequencies for [6O]fullerene appear at 272,
429, 495, 570, 772, 1099, 1250, 1422, 1467, and 1573.5 cm-1, with minor featwes at
266, 485, 711, and 1479 cm-1. The peak at 1479 cm-1 may be due to C60O. For
[7O]lllerene, the vibrational frequencies are at 226, 252, 259, 394,410, 417,430,456,
566, 700, 736, 1061, 1180, 1221, 1226, 1294, 1423, 1465, 1509, and 1562 cm-1, with
additional very weak features at 489,520,534,547, 1329, 1348, and 1365 cm-*.
No Raman spectra have been reported yet for higher fullerenes.
3 400 800
6oo nm
Figurn 11%b WMS spectra for [a]- and [7O]fullerenes recorded in heme, inset spectra are
recorded in benzene at higher concentration
44
5I L
n
m
-
1
.-
0"
L
Wavelength (nm)
W m w h g m (nm) 1
1.6. X-Ray Pow& Difiaction. Pure material gives the spectrum shown in the lower
trace of Figure 14.21Impure material always shows a shoulder to the left of the left-hand
peak, aa shown in the upper trace of Figure 14.
2. Solubility
This is a factor of particular interest to the synthetic chemist. Accurate
determination of solubilities is difficult, partly because saturated solutions are dark and
opaque, hence it is not easy to see if all the solid hllerene has dissolved. Also,a curious
feature is that the solubility passes through a maximum with increasing temperature.22
However, there is some evidence that the behaviour of (6O]lllerene in this respect
depends upon whether or not the sample has been baked free of solvent prior to carrying
out the temperaturdsolubility measurements.23 This aspect is still under investigation,
but it seems possible for example, that clustering (there is evidence that this exists in
soluti0n),2~may differ appreciably for baked- and unbaked samples. The close packing
in bakd samples could cause clusters to be solvated as such, the clusters then gradually
breaking up as the temperature of the solution is raised.
The solubilities of [60]fullerene have been determined in two studies and the
results (which are reasonably consistent) are shown in Table l.22,25 Data for
46
Table 1
Solub~tyof [60]fuUerene in mg/mL
Solvent Solvent
pentane 0.005,0.004 I methanol 0.000
hexane 0.043,0.040 1 ethanol 0.001
octane 0.025 I acetone 0.001
isooctane 0.026 I nitromethane 0.000
decane 0.071,0.070 I nitroethane 0.002
dodecane 0.091 I acetonitrile 0.000
tetradecane 0.126 I N-methyl-2-pyrroiidone 0.89
cyclopentane 0.0020 I dioxane 0.041
cyclohexane 0.036,O.OSl I pyridine 0.89
decalins (mix) 4.6 I tetrahydrofuran 0.000
cis-decane 2.2 I benzene 1.7, 1.44
trans-decane 1.3 I toluene 2.8,2.15
dichloromethane 0.26 I xylenes 5.2
chloroform 0.16 I mesityiene 1.5,0.997
carbon tetrachloride 0.32,0.45 I tetralin 16
trichloroethylene 1.4 I o-cresol 0.014
tetrachloroethylene 1.2 1 benzonitrile 0.4 I
dichlorodifluoroethane 0.020 1 fluorobenzene 0.59
1,1,2-trichlorofluoroethane 0.014 I chlorobenzene 7.0
1,1,2,2-tetrachloroethane 5.3 1 bromobenzene 3.3
tetrahydrothiophene 0.030 I 1,Zdichlorobenzene 27
2-methylthiophene 6.8 I 1,2,4-trichiorobenzene 8.5
carbon disulphide 7.9, 5.16 1 1-methylnaphthalene 33
I dimethylnaphthalenes 36
I 1-phenylnaphtfialene 50
I 1-chloronaphthalene 51
~~ ~
Table 2
Solubility of f70Jlllerene in m g / d
Solvent Solvent
pentane 0.002 J carbon tetrachloride 0.121
hexane 0.013 I benzene 1.30
heptane 0.047 I toluene 1.406
octane 0.042 I p-xylene 3.985
decane 0.053 I mesitylene 1.472
dodecane 0.098 I 1,2-dichlorobenzene 36.2
cyclohexane 0.080 I dichloromethane 0.080
acetone 0.019 1 carbon tetrachloride 0.121
isopropanoi 0.021
47
normally weak ESR signal @-value of ca. 2.0) that [60]Mlerene gives rise to, indicating
that this signal (which should be absent) is due to oxygenated i r n ~ u r i t i e sThe
. ~ ~probable
involvement of ozone and epoxide intermediates32 is supported by studies of direct
ozonolysis. One of these gave derivatives showing ketone, ester, and epoxide
pr0perties.3~A second study of ozonolysis of toluene solutions of the hllerenes showed
that both [60]- and [7O]lllerenes were rapidly oxidised at all temperaturesbetween -78
and +lo0 OC,giving monoxides, dioxides (and possibly higher oxides) with [60]fUerene
reacting faster than [70]fi~Uerene.~~ A similar study of [60]-, [70]-, [76]-, 1781-, and
[MJWerenes at 23.5 OC, showed that all were degraded by ozone ([7O]lllerene the
least rapidly) but oxides derived from [76]-,. [78]-, or [M]fullerenes were not
detected.37
Because both [60]- and [70]kllerenes have low-lying HOMOS, electrochemical
oxidation is quite dacult, but has been achieved. The chemically reversible oneelectron
oxidation waves (giving cation radicals with lifetimes >30 s) occur at 1.26and 1.20 v,
respectively, and for [70]fUllerene a second one-electron oxidation takes place at 1,75 v,
giving a di~ation.~*
added depends on the extent to which the solvent either donates electrons to the cage, or
accepts them from it.45 Thus [60]fullerene has good oxidising properties and may
oxidise d i y other materials in which it is contact. For example, it will oxidise
hydrogen eulphide to sulphur.46 Hydrogenated fillerenes are readily oxidised, but this
tendency is markedly reduced ifthey are free fiom the parent fillerene (Chap. 4), which
again points to the oxidising behaviour of the parent.
5. Mbedianeous Propertits
Some useful data for [6O]fillerene are the following:
Mean diameter, 6.83 4 outer diameter, 10.18 A; inner diameter, 3.48 A;
average C-Cdistance 1.44 A FCC (fbce-centred cubic) lattice constant 14.17 A.
Mass density, 1.72 g cm-1; molecular density, 1.44 x 1021 cm-3;; thermal
conductivity (at 300 K), 0.4 W mK-1; phase transition temperatures, 90 K, 260 K.
Binding energy per atom, 7.4 eV; electron affinity, 2.65 eV, 1st ionisation
potdid, 7.58 eV; 2nd ionisation potential, 1l.S eV; HOMO-LUMO band gap, 1.7 eV.
Rotational rate at room temperature, c4. 1 x. 1O1O s-l. Although this has
prevented a single cxystal X-ray structure being obtained for the free molecule, structures
have been obtained by using various complexes (which thereby reduce the rotational
rate), r.g. with benzene$7, ferrocene$* Sg,49 and i o d i n d t ~ l u e n e . ~ ~
[7O]Fullerene is also rotationally disordered at romm temperature.
References
3379.
23. A. L. Smith. personal communication.
24. V. N. Bezmelnitsin, A. V. Eletskii, and E. G. Stepanov, J. Phys. Chem., 98 (1994)
6665.
25. N. Sivaraman, R. Dhamodaran, I. Kaliappan, T. G. Srinivasan, P. R.Vasudeva Rao,
and C. K.Matthews,J. Org. Chem., 57 (1992) 6077.
26. N. Swaman, R.Dhamodaran, I. Kaliappan, T. G. Srinivasan, P. R. Vasudeva Rao,
and C . K . Matthews, Fullerene Science and Technology, 2 (1994) 233.
27. P. R Bukett, A. D. Darwish, H. W. Kroto, G. J. Langley, R. Taylor, and D. R.M.
Walton, J. Chem. Soc.,Perkin Trans. 2, in press.
28. C. J. H.Crowley and R Taylor, unpublished work, C. S. Sundar, A. Bharathi, Y.
Hariharan, J. Janaki, V. S.Sastry, and T. S . Radhakrishnan, Solid State Comm., 84
(1992) 823.
29. I. -our, J. P.Hare, H. W. Kroto, and R. Taylor, Lunar Plunet. Sci. Con$ XUZ,
(1991) 445; M.Gevaert and P. M. Kamat, J. Chem. Soc.,Chem. Commun., (1992)
1470; H.S. Chen, A. R.Kortan, R.C. Haddon, and D. A. Fleming, J. Phys. Chem.,
96 (1992) 1016.
30. T. Ark, Y.Murakami, H. Suematsu, K. Kikuchi, Y.Achiba and I. Ikemoto, Solid
Stute Comm., 84 (1992) 827.
31. A. Datta, R.Y.Kelkar, P. Borojerdian, S. K. Kulkami, and M. Datta, Bull. Chem.
Soc.Jpn., 67 ((1994) 1517.
32. R.Taylor, J. P. Parsons, A. G. Avent, S.P. Rannard, T. J. Dennis, J. P. Hare, H. W.
Kroto, and D. R. M. Walton, Nature, 351 (1991) 277.
33. J. M. Wood, B. Kahr, S.H. Hoke, H. L. Dejatme, R.G. Cooks, and D. Ben Amotz,
J. Am. Chem. Soc., 113 (1991)5907; K. M. Creegan, J. L. Robbins, W. K. Robbins,
J. M. Millar, R.D. Sherwood, P. J. Tindall, D. M. Cox, A. B. Smith, J. P. McCauley,
D. R Jones, and R.T. Gallagher, J. Am. Chem. Soc.,114 (1992) 1103.
34. M.Gevaert and P. N.. Kamat, J. Chem. Soc., Chem. Commun., (1992) 1470.
35. S. Kawata, K. Yamauchi, S. Suzuki, K. Kikuchi, H. Shiromaru, M. Katad, K. Saito,
I. Ikemoto, and Y.Achiba, Chem. Letf.,(1992) 1659.
36. R.Malhotra, S. Kumar, and A. Satyam, J. Chem. Soc.,Chem. Commun., (1994)
1339.
37. D. Heyman and L. P. F. Chibante, Red. Trav. Chim. Pays-Bas, 112 (1993) 531,639.
38. D. Dubois, K. M. Kadish, S. Flanagan, and L. J. Wilson, J. Am. Chem. Soc., 113
(1991) 7773; Q. Xie, F. Arias, and L. Echegoyen, J. Am. Chem. Soc.,115 (1993)
52
9818.
39. J. W. Arbogast, A. P. Dmanyan, C. S. Foote, Y. Rubin, F. Diedench, M.M.
Alvarez, S. J. Am,and R. L. Whetten, J. Phys. Chem., 94 (1991) 11; J. W. A h g u t
and C. S. Foote, J. Am. Chem. Soc., 113 (1991) 8886; R. R. Hung and J. J.
Grabowski, J. Phys. Chem.,95 (1991) 6073; Chem. Phys. Left., 192 (1992) 249.
40. H. Tokuyama, S. Yamago, and E. Nakamura, J. Am. Chem. Sue., 115 (1993) 7918;
A. S. Boutorhe, H. Tokuyama,M. Takasugi, H. Isobe, E. Nakamura, and C . Hblhe,
Angew. Chem. Intl. Edn. Engl., 33 (1994) 2462.
41. K. C. Hwang and D. Mauzerall, Nurure, 361 (1993) 138.
42. W. A. Scnvens. J. M. Tour, K. E. Creek, and L. Pirisi, J. Am. Chem. SOC.,116
(1994) 4517.
43. H.Tokuyama and E. Nakamura, J. Org. Chem., 59 (1994) 1135.
44. M.Orfanopoulos and S Kambourakis, TetrahedronLett.,35 (1994) 1945.
45. D. Dubois, K.M. Kadish, S. Flanagan, R. E. Haufler, L. P. F. Chibante, and L. J.
Wilson, J. Am. Chem. Sue., 113 (1991) 4364; Q. Xie, E. Perez-Cordero, and L.
Echegoyen, ibid., 114 (1992) 3978; D. Dubois, G. Moninot, W. Kutnet, M.T.
Jones, and K.M. Kadish, J. Phys. Chem., 96 (1992) 7137.
46. A. D. Darwish, H. W. Kroto, R. Taylor, and D. R. M. Walton, Fulferene Science
and Technology, 1 (1993) 571,
47. M.F. Meidine, P. B. Hitchcock, H. W. Kroto, R. Taylor, and D. R. M. Walton, J.
Chem. Soc.,Chem. Commun., (1992) 1534; A. L.Balch, J. W. Noll, and M.M.
Olmstead, ibid., (1993) 56.
48. J. D. Crane, P. W. Hitchcock, H. W.Kroto, R. Taylor, and D. R. M. Walton, J.
Chem. Soc.,Chem. Commun., (1992) 1534.
49. G. Roth, P. Adelamnn J. Phys. i France, 2 (1993) 1541,
50. P. R. Birkett, C. Christides, P. B. Hitchcock, H. W. Kroto, K.Prassides, R.Taylor,
and D. R. M. Walton, J. Chem. Soc.,Perkin Trans. 2 (1993) 1407.
Chapter 4
Hydrogenated Fullerenes
Paul A. Cahill
Chemistry of Organic Materials Department
Sandia National Laboratories
Albuquerque, NM 87185-0368 USA
1. Introduction
Pulletme hydrogenation yields fundamental information about the kinetics and
themdynamics of addition to these soluble, strained, aromatic molecules. Steric effects
in hydmfidlerenes are minimal, and their IH nuclei are excellent NMR probes for rapid
structutaf analyses of product mixtures. In addition, aspects of the chemistry of fuIletene
derivative8 that would only be available through extensive experimentation, if at all, have
been revealed through ab initio Hartree-Fock calculations.
This chapter is a critical review of both experimental and theoretical reports 'on
hydrogenated fullerenes and has the goal of revealing the nature of chemoselective
hydrogen addition. Many reagents have been reported to reduce fullerenes to yield
mixtures of products with stoichiometries up to at least h H 3 6 . Separations of mixtures
of C a b are often tedious even on specially designed high resolution HPLC columns.
These derivatives are typically stable toward at least brief exposure to air. Several
significant gaps in our knowledge exist, e.g., structure and energy data for C,=j0Hzn and
C70Ha isomers (n 2 3). and heats of hydrogenation for hydrofullerenes generally.
(Table 1). [Many nomenclature systems for addended fullerenes have been proposed.
The term hydrofullerene is preferred over the commonly used term fullerene hydride.
The generally accepted numbering is used throughout.f2 See Figures 1 and 2.1 No
qualitative difference between the semiempirical and ab initio results exists for CmH2,
but the isomer energy differences are striking. Semiempirical calculations require
relatively little computing power, but are unreliable for predictions of isomer energy
ordering (see below). Therefore, more expensive fully geometry optimized ab initio
H a w - F o c k (HF) calculations and 3-21G and 6-31G* basis sets (20-200 Cray Y CPU
hourdgeometry optimization) have been used to study the most interesting isomers. In
order of increasing energy, the favored addition patterns can be described as:
(1) 1.2-addition to a 6,6-ring fusion (also known as an interpentagonal bond)
(2) 1,Caddition to a 6-ring (1,4-CmH2). and
(3) 2.6-addition to a naphthalene subunit (1,16 -C&H2).
55
a
b
d' (4)
b' (di)
a' (I/)
Figure 2. Addition to the 1,9-, 7,B- and 21.42 carbons of C70 (shaded) lead to the
three lowest energy isomers of C7oH2.
Three conclusions can be drawn from theoretical results on the basis of excellent
agnemMlt between HF/6-31G* calculations and experiment (Table 1):
(1) the difference between the single and double bond character of the 5,6 and
6,6 ring fusions is 24 kcaYmol (HF/6-31G*), that is, all ring fusions are intermediate
between single and double bonds,
(2) the lowest energy patterns of addition to Cm are those local to one region of
the s p k e and follow from addition to double bonds located at the 6.6 ring fusions, and
relative isomer energies do not appear to correlate with the number of double bonds
localiusd by addition to 5.6 fusions, and
(3) semiempirical calculations and ab initio calculations are qualitatively, but
not quantitatively, consistent. That is, where large isomer energy differences are
observed (e.g. > 8 kcal/mol), semiempiricalcalculations reveal trends only.
56
The most favorable patterns of addition to C70 are more complex than those for
CaO because of its lower symmetry which results in 143 possible C70H2 isomers. AU 143
isomers have been evaluated with semiempirical methods and were found to be minima
on the potential energy surface, but only the four lowest energy isomers were geometry
optimized with ab initio methods. In order of increasing ab initio (where known) and
then MNDO-PM3 calculated energies (Table l), the lowest energy patterns of addition to
C70 are:
(1) 1,2-addition to the 6.6-ring fusion at the poles, closely followed by
(2) 1,2-addition to the 6.6-ring fusion at mid-latitudes ("c" layer),
(3) 1,4-addition (to "d,d " not "e" layer) the 6-ring that spans the equator
(4) two 1.4-additions to the 6-ring near the poles
( 5 ) .t3-addltlon
' ' to the 6-ring at the pole, and
(6) 1,Zaddition to the ' at low-latitudes ("d" layer).
Based on the structural similarity between Ccjo and C70, patterns (1). (2) and (4) were
expected, but the three underlined findings were unanticipated. Addition to the 21,42
carbons is strongly favored and would yield products functionalimd across (not dong)
the C70 equator. This 1,4 addition to what appears to be the most aromatic part of C70
was not suggested by bond order analyses and was totally unexpected. Bond order
arguments are consistent with pattern (6) as low energy K6kulC structures place double
bonds at this unique 5,6 ring fusion. Overail, qualitative simple arguments about the
patterns of addition to C a do not carry over uniformly to C70.
Unlie for CmH2, predicted isomer energy orderings are a function of the method
applied, with MNDO methods preferring the 7.8-isomer and ab initio HF/6-31G*
methods preferring the 19-isomer. Equilibration of 7,8- and 1,9-C7oH2 has yielded a free
energy of formation difference (MG) that is in quantitative agreement only with HF/6-
31G+ calculations (Table l)? and therefore the results of such calculations are proposed
57
C 7 d 2 1 9 s p 3 - s ~1.565
~ 1.588 1.583
7.8 sp3-sp3 1.546 1.567 1.565
(even at the semiempirical level) m l v 50 kcaVmol more stable than the corresponding
addition pattern to C a .
3. c
*
is a model for the chemoselectivity of multiple addition to C&o. The same
experimental and theoretical techniques that have been applied successfully to Ctj13I32and
C7oH2 have recently been applied to C&4. and as a result, the lowest energy patterns of
tetra-addition to Qo a~ now understood.15 These calculations have been extended to
Gj13(C!H2)2mwith similar results, and may also be applicable to derivatives of C70 and
higher fulferenes.
&Unless othexwise noted, CS2 and CgDg spectra are from Avent et a1.l4; c7D8
spectra are from references 1 and 2 (C@H2. C70H2) or 15 ( C d 4 ) .
bIn ref. 14, Table 1. this isomer was incorrectly labeled as the 1.2.57.58 isomer.
T h i s isomer was probably mis-assigned;l4this compound has been isolated.'S
dother CmH4 isomers have been identified, but structures have not been
assigned.14J5
61
3.2 ExperimentalInvestigations
Diimide or borane reduction of Cm or %H2 leads to C&4 and higher addended
products. Q H 2 is much less reactive toward further electrophilic attack by BH3 and this
may explain the large ratio ( > l o 1) of CmH2 to Q H 4 formed in the borane reduction of
c60 at Oo C. Hydroboration does yield CaH4 from C6oH2 at room temperature.
Diimide, however, is much more convenient for larger scale preparations.14
The &H4 product mixture contains at least 6 of the 8 isomers that would be
expected from two 1.2-additions to 6.6 ring fusions.14~15 Not all of these isomers are
separable by HPLC because many either isomerize or decompose during the multiple
elutions required for separation on a Buckyclutcher I column. Furthermore, the structures
of 5 of the isomers cannot be determined solely by 1H N M R because similar AB spectra
are expected. Three products, however, isomers 1.4, and 8 can be unequivocally
assigned based on their 1H NMR spectra, although the assignment of 8 depends only on
the observation of a singlet in the NMR spectrum of the CaH4 HPLC fraction.
A mixture of CmH4 isomers have also been equilibrated over a platinum
catalyst.15 A quantitative comparison with theory is not possible because only the
62
4. C60Hzn, n > 2
Of the more highly hydrogenated Cm derivatives, only GjoH36 (the molecule
which as the first reported derivative. signaled the beginning of fullcrene
functionalization chemistry)z2 and c&18 have been carefully studied. Unlike these
species, both the early members of the series, e.g., C&6 and C&8. and the more
highly hydrogenated products, i.e., H38 and above, are difficult to isolate in pure form.
The end member of this series, CmHm, is probably ring-opened because a closed-cage
geometry wouId be extremely strained. (Alternate Iow energy structures for an intact-
cage form of C m H a may involve endohedral C-Hbonds which may not be accessible
experimentally).
Computational studies of c4@6,CmH8, etc., have largely been limited to
semiempirical methods that have been shown to predict the wrong isomer energy
ordering for WQ.Unfortunately, more reliable ab initio calculations are available for
only a handful of isomers. A few low-energy structures of C&6 have been evaluated
using ab initio computational techniques by bootstrapping from 1,2,3,4-C&I4.6~15 Initial
HF/3-2 IG studies have shown that 1,2.3,4,5,6-C&6 (complete hydrogenation of a
cyclohexatriene ring, leading to a singlet in its 1H NMR) is not the lowest energy isomer
(1,2,3,4,17,18-&H6, the only other isomer examined to date. is 7.5 kcaUmol more
stable).33 Stepwise extension of this approach to C&8, etc., may yield insight into the
structure and relative heats of formation of more highly addended fullerenes.
Mixtures of isomers of the intermediately hydrogenated products have been
observed under many conditions, similar to the multiple Q3H4 products formed under
kinetically controlled conditions. The broad resonances observed by 1H NMR in the
spectra of these mixtures are consistent with the large number of possible kinetic
products. Isomerization to a thermodynamic mixture has not been reported.
Of the approximately loi3 isomers possible for C 6 0 H 3 6 . ~the ~ apparent
thermodynamic and kinetic stability of CmH36 is most intuitively explained by a
structure with T symmetry in which hydrogenation takes place so as to leave four
benzene rings intact.35 Such a structure would be consistent with the formation of
ctjoH36 in high yield under many conditions. However, alternate high symmetry
structures have also been considered (Th,s6, and D3d). and incorporate as many as two
intact arene r i n g ~ . ~ ~ Although
-~O the computational techniques applied to C60H36
isomers have not been as rigorous as those applied to the C6oH2. etc.. the results clearly
show that the T structure is likely to be the thermodynamically most favored isomer. The
most reliable calculations indicate that this structure -- the one with intuitively the
greatest stability -- is approximately 10 kcaVmol more stable than the next lower energy
isomer (S6. "LDF theory), and up to 97 kcaVmol more stable than the Th isomer (BLYP
method with double-zeta basis).37
-Hi8 and C&36 are formed in high yields under more forcing conditions than
the lower hydrogenated compounds and appear to be islands of rhermodynamic stability,
63
5. c 7 @ n~2 2
Calculations on isomers of C7oH4 and more highly hydrogenated C70 species
have ban Limited to molecular mechanics and semiempirical techniques, both of which
haw btan shown to be unreliable for addended fullerenes. especially in c a w of relatively
small tmcrgy differences. Given the favored local addition pattern for C&4. the lowest
energy isomers of C7& are likely to fall into patterns constructed from either the two
lowest energy isomers of C7@2 or from H2 addition to both poles of the molecule.
Ttris boot-strapping thought process can be extended to C7@6 and beyond, but
unlike Cm, in which 1.2 additions are favored by 7.6 kcaYmol over 1.4 additions, 1.4
additicm to the 21,42 carbons which span the C70 equator is predicted to result in products
only 4.5 kcdmol greater free energy than those observed from 1.2 addition. Steric
requimments of addends other than hydrogen will therefore be much more important in
multiple additions to C70 than to.&t Furthermore, speculations based on the established
energetics of suggest that (1) addition to one pole of C70 will not strongly affect
additian to the other pole, and (2) the lowest energy isomer of C7@4 will probably be
analogous to i.e., either 1,5,6,9-C7oH4 or 1.7,8,9-C7oH4.
Experimentally, C70H4 products analogous to 1,2,3,4-C(j& have been observed
in the QIimidereduction of C70 (Table 3).*4 Much more highly hydrogenated derivatives
of C70 have been reported.l*
6. C&Ih, m70,n 2 1
Hydrogenation of higher fullerenes has not been reported. The paradigm that the
lowest energy products of addition will result from 1,Zaddition to electron deficient
double bonds is likely to hold for these fullerenes. Hiickel calculations of n bond orders
of th- compoundsl4 are likely to be an excellent guide to 1.2-additions. but ab initio HF
calculations will be needed to gauge accurately the relative energies of the large number
of low energy isomers that may result from 1,2-. 1.4-. or other unique patterns of
addition.
64
7. Summary
Studies of hydrogenated fullerenes have provided fundamental insights into the
inherent reactivity and stability of addended fullerenes. Studies of these "simplest
hydrocarbon derivatives" have demonstrated that additions to fullerenes are under lrinetic
control. The most stable isomers that result from single or multiple additions to C a and
C70 indicate that the individual fullerenes have unique chemistry despite their structural
similarity.
8. Acknowledgments
This work was supported under the Laboratory Directed Research and
Development (LDRD) program at Sandia National Laboratories by the U.S. Department
of Energy under contracts DE-AC04-76DP00789 and DE-AC04-94DP85000. The
assistance of co-authors of previous works: R. A. Assink, K.T. Gillen, S. J. Jacobs, C.
M. Rohlfing and especially C. C. Henderson is greatly appreciated. S. Cole, R. Milberg,
S. Mullen, C. Welch and D. R. Wheeler were significant contributors to this project. C.
Henderson's careful editing is also greatly appreciated. I also thank A. Hirsch for
providing a pre-print of his review of fullerene hydrogenation which will be published in
his m0nograph.~2Finally, I would like to thank R. Taylor for the invitation to contribute
to this volume and his careful editing.
9. References
1. C. C. Henderson and P.A. Cahill, Science 259 (1993) 1885.
2. C. C. Henderson, C. M. Rohlfing, K. T. Gillen, P. A. Cahill, Science 264 (1994)
397.
3. C. C. Henderson, C. M. Rohlfing, P. A. Cahill, Chem Phys. Lett. 213 (1993) 383.
4. N. Matsuzawa, D. A. Dixon. T. Fukunaga. J. Phys. Chem 96 (1992) 7594.
5. C. C. Henderson and P. A. Cahill, Chem Phys. Lett. 198 (1992) 570.
6. N. Matsuzawa, T. Fukunaga, D. A. Dixon, J. Phys. Chem. 96 (1992) 10747.
7. H. R. Karfunkel and A. Hirsch. Angew. Chem Int. Ed Engl. 31 (1992) 1468.
8. C. C. Henderson and P. A. Cahill, presented to the Materials Research Society,
December 1992.
9. K. Hedberg, L Hedber, D. S. Bethune, C. A. Brown, H. C. Dorn, R. D. Johnson, M.
de Vries, Science 254 (1991) 410.
10. A. L. Balch, V. J. Catalano, J. W. Lee, M. M. Olmstead, S. R. Parkin, 1. Am
Chem SOC. 113 (1991) 8953.
11. D. R. McKenzie, C. A. Davis, D. J. H. Cockayne, D. A. Muller, A. M. Vasallo.
Nature 355 (1992) 622.
12. R. Taylor, J. Chem Suc. Perkin Trans 2 (1993) 813.
13. (a) A. G. Avent, A. D. Darwish, D. K. Heimbach. H. W. Kroto, M. F. Meidme, J.
P. Parsons, C. Remars, R. Roers, 0. Ohashi. R. Taylor, D. R. M. Walton, 1.Chem
Soc. Perkin Trans 2 (1994) 15, ref. 9. .S. Ballenweg, R. Gleiter, W. Witschmer,
Tetrahedron Lett. (1993) 3737. (b) A. D. Danvish, H. W. Kroto, R. Taylor, D. R.
M. Walton, Fullerene Sci. Technol. 1 (1993) 57 1 and reference 16.
65
Long Y. Chiang
Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan
1. Introduction
Fullerenic truncated moleculesly2 represent an intriguing new class of carbons,
which have attracted the attention of chemists interested in exploring the fbndamental
properties of these novel materials, both as molecular entities and as an anchoring base
or building blocks essential to the design of specialty chemicals and polymers. The
increasing availabiity of fiillerenes with reproducible quantity, and lower costs, has
encouraged more research and development effort targeted for potential technological
applications. In the past three years, intensive research activities have been focussed on
understandingthe distinguishing physi~al3'~ and chemical6 properties among C60, C70,
and higher fbllerenes. The molecular behavior of C6o in the solid state is important for
prediction of reliable specialty hnctions in the application of synthesized C6o-contahhg
organics and polymers. Most of the important physical phenomena observed for C6o
Werenes can be correlated to their fbndamental characteristics of molecular electronic
structure associated with highly degenerate orbitals in an Icosahedral (Ih) sy~nmetry.~
Therdore, the electronic and optical properties of c60 hllerenes and the associated
lllerides are dictated by the ground state electron population in both the triply
degenerate tiu set of molecular orbitais (LUMO) and the quintetly degenerate hu
molecular orbital set (HOMO).3 Most of the interesting solid state properties of
compounds comprised of C6o and electron-donating materials originate mainly from
their high electronegativity. The electron transfer from strong molecular or polymeric
donors to C6o gives anionic species, exhibiting superconductivity,4 semiconductivity, or
enhanced magnetic properties8 in crystalline solids.
In the case of weak organic or polymeric electron donors, the electron transfer
from donors to fullerenes can be realized by photo-initiation. The photo-induced
formation of exciplexes of the singlet excited state of C70 molecules with N,M-
diethylaniline in methylcyclohexane at room temperature was reported by The
photo-induced electron transfer from a highly conjugated conducting polymer with a
67
68
number of reactive polar fknctional groups, especially terminal hydroxyl and Smine, form
a new class of supercross-linking agents suitable for the fabrication of polymer networks
(see also Chap. IS). The high incidence of star-shape cross-linking among polymer
chains in the matrix network may alter significantly the physical and mechanical
properties of the resulting thennosettig polymer products.
A A Functlonalizedfullerene derivatives
as versatile intermediates
A -OH, -NH,, -OR, -NHR.
-OCOR, -NHCOR.
threshold (> 7.61 v24of neutral C a molecules greatly hindered the attempt to
generate a higher oxidation state of C60. The observed high electron aftinity of C6o
compared to its electron-donating ability leads to the prediction that this class of
materials is more susceptible to nucleophilic additionsz5 than to electrophilic additions
-
(Figure 2).
Electron
Oxidation
/
Nucleophilic
1
h
Electron Additions
Reduction
- EQ
Electrophilic
Additions
bffu
0
- Nucleophilic
Replacement Nu
Nu
U
Nu
and chlorinated35J6 derivatives, and the addition of benzene and toluene in the presence
of aluminium chloride.3'
The high reactivity of hllerenes towards attack of other electrophiles in the
presence of nucleophilic reagents, such as water or carboxylic acids under mild reaction
conditions, has been demonstrated re~ently.38~1 The observed nucleophilicity of
fullerenes in terms of their vulnerability to electrophilic additions compensates for
difficulties that have been encountered in achieving hrther hnctionalization of C a
molwuh via electronic oxidation. This enables the use of olefinic moieties of C6o as the
reactive electron-rich sites for reactions. This chemistry enriches the scope of synthetic
methodoloey for fbllerene derivatization, and provides practical routes for the
preparation of c60 derivatives with multiple polar functional groups such as hydroxyl
and wboxylate groups, leading to an enormous variety of novel fullerene derivatives.
'"his type of electrophilic approach involves the addition of strong electrophiles
acros~the oletinic moieties of fillerene molecules, forming cationic intermediates as
shown in Figure 2. These intermediates are decomposed in situ by weak nucleophiles to
afford Werene derivatives containing multiple hnctional groups. Utilization of this
synthetic skategy has been exemplified in the reaction of C6o with either a mixture of
sulfuric kid and nitric acid in aqueous solution,38~39or nitronium tetrdu0roborate4~in
ordcr to synthesize water-soluble polyhydroxylated hllerene derivatives (fullerenols, 1).
Both the acid- and the nitronium chemistry transform the instability of the resulting
cationic intermediates into highly reactive intermediates suitable for derivatization.
In the former case, these intermediates can be converted, in the presence of
water, directly into polyhydroxylated fullerene derivatives. This type of reaction is best
carried out at 85-95 "C in a solution of sulhric acid, potassium nitrate and water without
any hydrocarbon-containing reagents. Potassium nitrate was utilized as the precursor for
generating Ntric acid in situ. The resulting polyhydroxylated hllerene derivatives are
highly soluble in an aqueous acidic medium, but precipitate fiom basic media when the
pH ofthe solution higher than ca. 9.0 This unusual solubility property of hllerenols
facilitated isolation and purification of the nearly salt-free products. The lllerenols were
charaeteriaed as containing an average of 14-15 hydroxyl groups per molecule.
In the latter case, nitronium tetrafluoroborate was used as an electrophilic reagent
to activate olefinic bonds of the lllerene prior to the in situ nucleophilic addition of mild
nucleophiles, such as arene- or alkylcarboxylic acids, in a non-aqueous medium. The
72
-
2 (The representativehemiketal structureof fitllerenols 1)
The structure of fillerenol 1 prepared either from the aqueous acid chemistry or
from the nhronium chemistry was characterized and found to consist of several hemiketal
carbons (Z), each linked with enol-ether and incorporated as a part of the expanded
lllerene cage, in addition to the tertiary hydroxyl gr0ups.~3These particular fiuictional
moieties can be viewed as hydroxylated fullerene oxides.& Evidence for the hemiketal
structure was given by the observation of chemical shifts of vinyl ether carbons and ketal
carbons centered at S 170.3 and 100.0, respectively, in the 13C NMR spectrum of
fbllerenols 1. Conclusive verification of the presence of hemiketal knctions in fullerenols
73
corresponding
1 was provided by the reversible interconversionof these moieties to the
ketone upon variation of pH in aqueous solution, and this is contrary to the case of
fililerenoi 3.
(Fullerenols, t)I
filtered through Celite to remove any unreacted fullerene particles. Neutralization with
NaOH to precipitate products followed. Full precipitation was achieved at pH > 9.0. The
resulting fine amorphous brown solid was moderately soluble in water and very soluble
in aqueous acids at pH < 5.0 . In general, the thorough removal of water from partidy
hydrated products in vacuum at 50 OC affords a brittle brown solid with a slightly lower
solubilii in water. However, its solubility in acidic water remains unchanged.
The product yield of this hydroxylation reaction was estimated to be greattr than
95%, with only a trace amount of starting C6o recovered. This is attributable to the
partially hydroxyl-added lllerene intermediate having a higher solubility in acidic water
than the unreacted hllerene itself Thus, the reaction tends to continue on the
intermediate until completion. The elemental analysis of samples from several batches
showed a high oxygen to carbon ratio of 0.4 to 0.5 with only a trace quantity of nitrogen
(< 0.6% by weight). Because of the high compatibility of polhydroxylated lllerene
derivatives 1 with sodium sulfate in aqueous solution, the product often contained one to
several sulfate molecules per fillerene derivative, in addition to water fiom the workup
procedure. Further purification by redissolving them in dilute hydrochloric acid (0. lN),
followed by reprecipitation after neutralization with NaOH, teduced the sodium sulfate
level to a minumum level of less than 0.1 molecule per fullerenol. Complete removal of
sodium sulfate can be achieved by repeating the above procedure or by washing the
product with dilute NaOH solution.
The IR spectrum of hllerenols clearly indicates the disappearance of the
characteristic C a peaks at 1428, 1183, 578, and 528 cm-1. A very strong hydroxyl
absorption band at 3424 cm-1 and three absorption bands centered at 1595, 1392, and
1084 cm-l are evident as shown in Figure 3a. The broad absorption band is due
presumably to the heterogenous nature of the product. Several conventional soft
ionization techniques have been used for the mass spectrometric study of fidlerenols. No
molecular ions of products were captured. For example, when the desorption electron-
capture ionization technique was used, only C6o and C70 anions were observed in the
spectrum. The fullerenol sample was dissolved in H20 and filtered through Celite prior
to measurement. Since the fbllerenes are themselves not water soluble, the presence of
C6o and C70 anions in the negative ion spectrum is apparently a result of thermal
decomposition of fullerenols occurring during the desorption process. The spectrum is
also indicative of the products being C6o derivatives.
75
I I I I I I I 1
4 a a o ~ 3 w o ~ 2 0 0 0 lsoo loo0 wo a n - 1
Fvrpvc 3. The IR spectra of (a) fullaenols, (b) 4, the products of reaction of Nlerenols with 5-
bromovaleryl chloride, and (c) the products of reaction of Nlerenols with 4 - b r o ~ acid
~ c
c60 was observed. The large shift indicates that in hllerenols, a higher percentage of
cazrbons are in a high oxidation state compared to the parent fillerene. Simplecurve-
fitting analysis of the hilerenol carbon peak (curbve c of Fig. 4) indicates the presance of
more than two different carbon oxidation states, assuming that the first peak matches
with the lower binding energy region of the experimental curve.
10
9
8
7
ul
..6
- 5
$ 4
3
2
1
298 296 294 292 290 288 286 204 282 280
Binding energy f eV
Figure 4. The x-ray photoelectron (XPS) spectrum of the Ctsbinding energy of hllerenols ( m u ) ,
Cm fuilerene (curve b), and the curve-fitting anatysis for non-oxygenatedhrllerenes
(curve c) in fuilerenols showing higher oxidation statesof &XIS in 6
600 940 1280 1620 1960 2300 2640 2980 3320 3660 4000
ml I
Fignre5. The mass spectmm of 4, obtained using the laserdemqxiontechnique and a 4-hydroxyu-
cyanocinnamic acid matrix
distinct peaks at m/z 720 and 840 respectively represent the c60 and C70 frasment ions
arising from laser ablation of 4. A broad unresolved distribution of ions ranging f?om d z
940 to 1900, centered at m/z 1425 was observed in Figure 5. The spectrum is comktent
with an average molecular weight for 4 since C~~(-~CO-CH~CH~CH~CH~B~)~(O 2
requires m h = 1464. The higher end o p h e ion distribution ( d z 1840-1875) represents
the upper limit of the molecular weight distribution of 4, and corresponds to 8 C6o
molecule possessing 18-20 hydroxyl groups and five 5-bromovaleryl ester group4 and
thus an initial total of 23-25hydroxyl addends per molecule.
In summary, fillerenols 1, synthesized by the aqueous acid method, have been
characterized to contain, on average, 14-15 hydroxyl addends per C6o molecult. The
chemistry has demonstrated high reactivity of lllerenes towards electrophilic attaok in a
reaction medium containing both an electrophilicreagent and a mild nucleophilic reagent.
Hypothetically the reaction involves the electrophilic addition of nitronium ion to the
olefin moieties of the Mlerene, followed by nucleophilic substitution with water to
introduce the hydroxyl groups onto the fidlerene as shown in Scheme 1.
w h
200 NO 160 140 la t i 10 do ;o ;D ppn
Figure 7. 1% NMR spcaxa of (a) pbromdbcnzoic acid and (b)the lllerene derivative 8b in THF-dg
showing both hydmxylatedandp-bromobenzoatecarbon peaks
0 1 ppm downfield shift From the corresponding protons (two sharp doublets at 6 7.56
and 7.83)in tert-butyl p-bromobenzoate. Upon treatment with D20, the broad peak of
hydroxyl protons ( G O B centered at 6 4.25 disappeared (Figure 8c) and a new sharp
peak of water protons at 6 3.90 was obtained. From the proton integration in FigUtes 8a
and 8b, the ratio between the number of hydroxyl protons and the total number of
aromatic p-bromobenzoate protons was determined as 0.65 and 0.78, respectively.
Elemental analysis of compound 8b indicated a carbon:bromine ratio of 20, which
corresponds to an average chemical composition for 8b of 4-5 p-bromobenzoate
83
addends par CfjO molecule Overall, this indicates in the structure of 8b, an average of
13-15 hydroxyl addends and 5 p-bromobenzoate addends per C6o molecule. Thus the
hydrolysis of 8b in aqueous alkaline solution should give the corresponding water-
solublefwiarenols 1, having an average of 18-20 hydroxyl groups per c60 molecule.
The IR spectrum of Mlerenols 1 (Fig. 6c) showed a strong broad hydroxyl
absorption band centered at 3432 cm-1 and three broad absorption bands centered at
1590, 1380, and 1045 cm-1, closely resembling those in the IR spectrum (Fig. 3a) of
lllerenols prepared by the aqueous acid chemistry. Mass spectroscopic study of 8b was
perfonntd using the fast caesium-ion bombardment [or liquid secondary ion mass
spectromq (LSIMS)] technique. A VG ZAB-T four sector instrument was used for the
positive LSIMS experiments. Prior to the FABILSIMS analysis, fullereme derivative 8b
were 6ltertd through Celite, and deposited on a matrix of (3:l) dithiothreitol and
dithioeaythritol. The matrix was bombarded by a Cs+ ion beam (35 kev). The positive
ion FABILSIMS spectrum of 8b (Figure 9) shows that the most abundant ions are
centered at m/z 720. There are many ion clusters above d. 720 separated by multiples of
16 (0),17 (OH), or 18 (OH2) mass units, providing evidence of oxygen entities in the
molecule. Ion clusters of higher fbllerenes, presumably generated by the carbon
recombmtion of fragments under the MS conditions, were observed above m/z 900.
The much lower intensity of ion fragments above nu'z 1500 indicates the fast
cleavage of p-bromobenzoate moieties upon caesium ion bombardment. However, two
groups of ion fiagments with the highest mass peak at d z 1457, or 1473 were detected,
in good agreement with the mass of an ion of a C6o derivative with 2 pbromobenzoate
and 20 hydroxyl addends (m/z 1458) or 21 hydroxyl addends (m/z 1475), respectively. A
c o e v e weight loss of 17 mass units from an ion at m/Z 1458 (A+) was observed and
gave groups of ion fragmentations centered at m/z 1441 (A+-OH), 1424 (A+-20H),
1407 (A+-30H), 1390 (A+-40H), 1373 (A+-SOH), and 1356 (A+-60H).
Interestingly,the spectrum showed a secondary band with the highest mass peak at d z
1239 indicating a fragment derived fiom the dehydration of the ion at d z 1257, which
corresponds to a C60 derivative with one p-bromobenzoate, 18 hydroxyl, and two
epoxide (&om 1,Z-diol dehydration) additions. Further sequential loss of 17 mass units
from the ion at d z 1239 (B+) was detected and gave groups of ion fragmentations
centerad at m/z 1222 @+-OH), 1205 (B+-20H), and 1188 @+-3OH) These results
provide strong evidence supporting the characterized chemical composition of 8b.
84
E
"
L
I I t E
x7
9. The mass spechum (positive ion FAF3LSIMS) of the fullerene derivative 8b, prcparad from
pure c60. The mass of the highest ion peak in the fragmentation group is indicated. Ion
clusters of higher fullerenes, 24 amu (C2) apart, and generated presumably by the carbon
recombination of fragments under the mass spectrometryconditions, are marked by (c)
..
c60
9 Polycyclosulfated C, (x = 6-5 and y = 61)
10
-
Scheme 3. Synthesis of fullerenols by the hydrolysis of polycyclosulfated fullerene derivatives 9 under
mild conditions
86
suspended green solution was obtained immediately, indicating the existence of organic
radicals. Detection of these radicals in the EPR spectrum 28-30 provided clear evidence
of a reaction mechanism involving the electronic oxidation of C6o via initial formation of
its cation-radicals. Within 5 h of reaction, a visible change from a dark green to a brown
suspension was observed, revealing the limited stability of C6o cation-radicals in the
reaction medium. This instability enhances the reactivity of them towards addition of
suhric acid. At the end of reaction, the acid suspension was added dropwise to
anhydrous diethyl ether to precipitate polycyclosulfated fullerene products 9, as orange
soIids, as shown in Scheme 3. Hydrolysis of 9 in water at 85 "C or in aqueous & d i e
solution at ambient temperature afforded hllerenols 3 in an overall yield of cu. 80%
(from c60). The reaction proceeds with an efficient hllerene cyclosulfation followedby
partial hydrolysis, to give the corresponding hydroxy hydrogen-sulfate intermediate 11.
I II
II I
c . . , . . . . + . . . , . . . . , . . . . , . . . . , . . . . , . . . . , . . . . , . . . . ~ . . . . ~ .. - , . . . . a
12.0 11.0 10.0 4.0 8.0 7.0 6.0 5.0 4.0 3.0 20 1.0
-
0.0 ppm
fragmentation group was found at m/z 1129 and 1056 in positive and negative ion FAl3
mass spectra, respectively.
im 14
. ws m in ia (u t.1
.*LtUml.Vl
Figurn 12. The X-ray photoelectron (XPS spectrum of the SzP binding energy of (a) polycyclorulrated
fullerene derivatives9 (solid curve), Et2SO4 (dottedw e ) , and partially hydrogen sulfated
fullereno1 derivatives 10 (dashed curve); (bl) Et2S04; (b2) polycyclosulfated hllerene
derivatives 9. In Figures bl and b2, the curve-fittinganalysis (dottedlines is indicated inside
the experimental curves (solid lines). The binding energy in the spectra is not calibnted
provides insight into the structural nature of 3 and 9, and allows a fair determination of
the average number of hydroxyl addends on each hlierene molecule. In the analysis it
was assumed that the first fitted carbon peak matches hlly with the lower binding energy
region ofthe experimentalcurve, and then the second carbon peak was inserted to fit the
rest of the absorptions in the higher binding energy region. As a result, the spectrum in
Figure 138 for the cyclosulfated derivative 9 fitted in good agreement with a strong
absorption band of Cis bindmg energy, corresponding to the non-oxygenated carbons
(C-C), 04Iltered at 284.2 eV (76.6%) with a 111 width at half maximum (FWHM width)
of 1.6 eV, and the second absorption band, correspondingto mono-oxygenated carbons
(GO), centered at 286.3 eV (19.4%) with a FWHMwidth of 2.0 eV.
10 : : : : : : : . . : : : : : :-
6
7
w 6
--.
S
B 4
3
2
0
296 294 282 190 286 286 264 262 260
Blnding Energy (eV)
Fipn 13. The X-ray photoelectron (nS) specrnun of the ClSbinding energy of (a) polycyclosulfated
iblkrene derivatives9; (b)Mlerenols 3; (c) partially esteritled trinuoracety~lerenol
derivatives 12. The we-fitting analysis is indicated inside the experimental curves
band centered at 284.2 (74.6%) and 286.1 (20.2%)) with a FWHM width of 1.6 eV and
1.9 eV, respectively.
The atomic ratio between non-oxygenated carbons of 3 was found to be 47 : 13,
similar to that of 9. Further esterificationof 3,using trifluoroacetic anhydride as reagent,
afforded fbllerenol trifluoroacetates 12. The XPS data of 12 (Fig. 13c) showed a clear
four-band spectrum, with binding energy maxima centered at 284.2 (68.7%, FWHM of
1.7 eV), 286.3 (19.9%,FWHM of 1.9 ev), 288.8 eV (67.7%, FWHM of 2.4 eV, ester
carbons), and 292.0 (3.7%, FWHM of 1.7 eV, fluorinated carbons). The atomic ratio of
non-oxygenated carbons : mono-oxygenated carbons : fluorinated carbons of 12 is thus
47 : 13 : 2.5, which agrees reasonably with a partially esterifed fbllerenol structure
containing nine hydroxyl and three trifluoroacetoxy groups on average. The results
consistently support an average structure of fhllerenols 3 having a maximum of twelve
hydroxyl addends. In combination with the data obtained from elemental analysis and
spectroscopic measurements, it was conciuded that the structure of 9 can be described as
a poIysulfated hllerene derivative, containing a maximum of 5-6 cyclosulfate units.
Partial hydrolysis of 9 readiiy occurred during the work-up procedure to give chemical
characteristicsof hydroxyl and hydrogen sulfate functions.
Since the hydrogen sulfate moieties of the partially hydrolyzed compound 11
contains acidic protons, 11 was complexed with an excess of p-dimethylaminopyridine
@MAP) in DMF solution. Elemental analysis of the precipitated 11-DMAP adduct
revealed a C:S:N ratio of 39:1:2 corresponding to 1.9 DMAP units per C6o molecule.
The 1H NMR spectrum of the adduct in DMSOd6-DMFd7 solution (dried over
molecular sieves) showed distinguishable peaks at 6 8.13, 6.62, 3.34, and 2.98,
corresponding to the aromatic a- and J3-protons, hydroxyl, and methyl protons,
respectively. The hydroxyl peak was fbrther identified by deuterium exchange with D20.
From the integration ratio between aromatic and hydroxyl protons, more than 10
hydroxyl groups were estimated to be in the 11-DMAP adduct. These results also
support the above structural assignment of fhllerenol3.
below 180 "C was detected. It was followed by a strong aand sharp thermal evolution of
SO2 molecules at an onset temperature of 187 "C that extended to a maximum at
245 "C. The observed SO2 evolution fiom thermal treatment of compound 9 confirmed
the presence of cyclic sulfate 0-SO2-0- entities, cleavage of S - 0 bonds evidently
occuring. Other gases evolved in this temperature range included CO and CO2; the latter
may rev& the occurrence of structural rearrangement of radical intermediates in
conjunctionwith the SO2 elimination. Since the intensity of C 0 2 was significantly lower
than that of SO2 aand the intensity of CO was trivial, the major portion of material
weight loss (28%) at temperatures between 190 "C and 3 10 OC can be correlated to the
quantity of SO2 molecules eliminated. That allowed an estimate of slightly less than six
cyclosu&tc units per C6o molecule in 9,consistent with the X P S data.
Temperature ( O C )
Figure 14. TOA II~&FSspectrascopic data showing the percentage weight change (TG), differential
weight change (DTG), and the intensity of SO, evolved upon heating the polycyclosulfated
derivative9 at a rate of 6 "C/min
13 L4
%heme 4. Exclusion of cfjosultonation in the reactionof fullerenes with fuming sulfuric acid
did not lead to formation of sultone 13, as shown in Scheme 4. Rather, the primary
fbnction of sulhr trioxide molecules in this case is to promote one-electron oxidation of
hllerene molecules, forming a C6o cation-radical, as depicted in Scheme 5.
Trapping of the c60 cation 15 by anionic HSO4- or HS2O7- pISOq'(SO3)]
species affords the corresponding hydrogen sulphated C6o radical 16. Since the open
allylic carbocationic C6o radicals 15 are prone to rearrange, the formation of various
isomeric products is feasible. Further electron oxidation of the radical intermediate 16
yields the corresponding cationic hydrogen-sulfated c60, 17. Intramolecular cyclition
of intermediate 17 via the elimination of one proton produces the desired product of 1,2-
or 1,4-cycIosulfated C6o derivatives 9.
Unlike organic sulfonates which exhibit remarkable hydrolytic stability even after
prolonged heating, cyclosulfated C6o derivatives 9 with a -C-OSOz- linkage are readily
susceptible towards acid hydrolysis. It is noteworthy that the hydroysis rate for cyclic
sulfates can be 20 times as fast as that of open-chain dialkyl sulfates.49 Hydrolysis
proceeds mainly by the C-0 bond cleavage via the attack of water molecules at the
conjugated P-carbon, as depicted in Scheme 3, to yield fkllerenols 3 as the final product.
In summary, the novel cyclosulfation chemistry for the functionalization of
fbllerenemolecules, resulting in the DMF-soluble polycyclosulfated fkllerene derivatives
9, has been demonstrated.42 The cyclosulfation reaction of c60 was performed in neat
fuming sulfixric acid at 55-65 OC under N2. Hydrolysis of 9 either in the presence of
I@{
95
HzSO4-SO3
*
/ \
Electronic Oxidation
- - e-
s I7
Scheme 5. Hypothetical c60 cyclosulfationreaction mechanism involving stepwise electronic
oxidation
water at 85-90 "C or in aqueous NaOH solution at ambient temperature gave a high yield
of polyhydroxylated fbllerene 3, containing no hemiketal structure. The facile hydrolysis
of the cyclosulfated C60, 9, or the hydrogen-sulfated C6o during the purification
procedure often prevented accurate quantitative determination of sulfhr atoms. The
functional characteristics and quantity of sulfate moieties per C6o molecule in
polycyclosulfated fillerene precursors 9 and the structure of fbllerenols 3 were
determined mainly through analysis of the TGA-mass spectrum, and of two absorption
bands, correspondingto the binding energy of sulfbr (Szp) and carbon (C 1s), in the X P S
spectrum. The XPS spectrum was used to determine the oxidation state of sulfbr and the
quantity of carbons possessing a higher oxidation state than that of the unreacted
lllerenic carbons. As a result, an average of 10 to 12 hydroxyl addends in the structure
of lllereno13 was correlated to the structure of polycyclosulfated fullerene 9 containing
5 to 6 cyclosulfate units. Mechanistically the cyclosulfation reaction is apparently
initiated by a one-electron oxidation of C6o molecules, followed by the attack of anionic
sulfate species on the resulting c60 cation-radical intermediates, to give the
corresponding hydrogen-sulfated C6o radicals. Further electron oxidation and
96
correlated to the allylic oxidation of C-H bonds, catalyzed by singlet oxygen,53 of which
lllerene molecules are potent producers.54 The intermediate was then reacted with a
solution ofhydrogen peroxide followed by sodium hydroxide. The resulting mixture was
stirred for 3h and allowed to settle overnight. The toluene layer was removed to leave a
yellow-orange aqueous layer, together with a brown precipitate, which was separated by
filtration. The precipitate gave IR absorption bands at 3430, 1631, 1385, cu. 1090, aand
450-550 cm-I as shown in Figure 15, and these are commensurate with those of
lllerenol 1 and 3. The relative band intensities at 1632, 1385, and 1090 cm-* were
somewhat batch-dependent, but the similarity to the spectra shown in Figs. 3a and 6c is
most strilring. Other notable features include the absence of stretching bands.
The spectrum also showed a peak at 1788 cm-l which disappeared slowly upon heating
under vacuum. Therefore, this peak was believed to arise from acid chloride trapped in
the lattice of the fbllerene derivative. The heated materials gave a multiplet in the l H
NMR spectrum at 6 162.3, corresponding to the chemical shift of ester carbons. These
spectroscopicdate confirmed benzoate formation in the reaction.
Further experients were carried out in order to confirm the reactive role of
oxygen during hydroboration of fbllerenes. Two runs were performed in parallel, using
an excess of BH3-THF: one under nitrogen, the other in air. Only a small amount of
precipitate was obtained in the reaction carried out under nitrogen. The products of both
reactions were quenched with acetic acid, followed by sequential washing with water and
sodium carbonate. The isolated products from the reaction carried out in air showed an
IR spectrum similar to those of hllerenols. However, the IR spectrum of products
synthesized from the reaction carried out under nitrogen was quite different, and showed
the expected strong C-H stretching bands. These results substantiated the contribution of
oxygen in the reaction mechanism of C6o hydroboration, leading to the formation of
polyhydroxylated fbllerene derivatives.
I " " l ' " ' I " " l " " 1 " " 1 ' " ' 1 '
250 200 150 1W 50 0 -50 ppm
Figure 16. The I3C NMR spectrum of fulierenols1 obtained using: (a) solid-state CPlMAS at 3.8 Wiz
spinning speed,@) solid-state C P M S at 3.0 kHz spinning speed, and (c) in QO s1ution
100
three distinct carbon peaks with chemical shifts centered at roughly 6 80, 140, and 170-
180, and one weak carbon peak centered at 6 103.2. These spectra were reproduced in
D20 solution, showing two major bands with chemical shifts centered at 6 79.0 and
140.3, corresponding to hydroxylated carbons (C,) and unreacted olefinic carbon,
respectively, Due to the lack of carbonyl absorptions in the IR spectrum of fidlerenols
(Fig. 3a), which excluded ester or related enctions in 1, the third downfield band at 6
170.3 was assigned to the vinyl ether carbons (C,). The fourth weak band centered at 6
100.0 corresponds clearly to di-oxygenated carbons such as ketal (RO-C-OR) or
hemiketal (RO-C-OH) carbons. From the low probability of ketal formation on C6o it is
suggested that the di-oxygenated carbons in fillerenols 1 arise from hemiketal fbnction.
These spectra thus provide consistent evidence to support the structural characterization
of fullerenolsin terms of the presence of hemiketal functions with vinyl ether linkages.
34
-34
Figure 17. TGA-mass spectroscopicdata of Illerenois 1, showing the percentage weight change (TG),
differential weight change (DTG), and the intensity of H20,C0,aand C02 gases evolved
upon heating at a rate of 6 "Urnin
carbons is the main source of CO whereas the thermal cleavage of di-oxygenated carbons
leads to &a release of C02. As shown in Figure 17, the physically absorbed I420 (6% by
weight) can be e l i t e d below 200 OC. The subsequent evolution of water due to the
dehydration of polyol moieties of 1 was observed between 280 and 430 "C, indicating
the polyhydroxy nature of fullerenol. This chemical dehydration process corresponds to a
weight less of 8%. The thermal elimination of CO and C02 occurred in two stages
start& &om 450 OC with C02 as the major gas detected, and giving a combined weight
loss of 19%. For C02 evolution, peak maxima occurred at 555 and 700 "C, with much
higher evolution at the first stage. By contrast, the intensity of CO evolution was
relatively weak with peak maxima at 575 and 695 "C.
In a TGA-FTIR study of fillerenol 1 (Fig. 18), the intensity of the C02
absorption band in the IR increased to a maximum at 605 OC, whilst the onset
temperature for the detection of the CO absorption band was 650 OC with a peak
99.3
-
Ecn 5
s
ss a G
%
47.0
-8
no0 r*m noo 1 mrouconm,
Figure 18. "he TGA-IWR measurement of fullerenols 1, showing the temperaturedependent weight
loss and IR absorptionbands of H20, C02,and CO evolved upon heat treatment at a rate of
6 OC/min
102
maximum at 735 O C . The weight loss of fullerenol in the sample used for this experiment
was 14% and 27.5%, respectively, for chemical dehydration, and thermal loss of C 0 2
and CO. Figure 18 shows that the C 0 2 absorption band was detected in the IR
spectrum at a temperature as low as 175 "C. Since the thermal evolution of C02 from
the structural skeleton of fullereno1 involves cleavage of several sigma-bonds, it would be
expected that a temperature higher than 400 "C would be necessary to accomplish the
process. A conceivable explanation for the elimination of C 0 2 at low temperatures
involves a bond-cleavage initiation via the chemical dehydration of polyols, in
conjunction with thermal lability of the hemiketal structure.
1 (hemlketal moieties)
{*} Y
\ /
??
Scheme 6. Mechanisms for acid-catalysedrearrangements in fullerenols
vic-diols with acid can potentially be complicated by the Pinacol rearrangement, whereby
tertiary uic-diol moieties of 1 are transformed into the corresponding ketone 19, as
shown in Scheme 6. Differentiation between the hemiketal-ketone equilibriation, and the
Pinacol rearrangement of vic-diol under acidic conditions can be made through
examination of the full reversibility of the former interconversion, leading conceivably to
the formation of several different hydroxyketone moieties, represented as the partial
structure 21 in Scheme 6. Not only is the Pinacol rearrangement irreversible, but in the
present case it requires both cleavage and formation of carbon-carbon bonds in the
protonated structure of 18 to afford ketone f9 (which contains highfy strained tetracyclic
5,5,6,6-mmbered rings sharing a common carbon atom).
Fullcrenols with multiple tertiary hydroxyl groups were indeed found to be
sensitive to certain acid conditions (aqueous hydrochloric acid, or HBFq-Et20 in
methand). For example, lllerenol 1 was treated with dilute aqueous HCI (0.4 M) at
80 "C for 5-16 h. Suspended brown solids were slowly formed fiom an initially dark
brown solution. At the end of reaction, solids 2la were collected by centrifugation,and
Figure 19. The IR spectrum of: (a) fullerenols 1; (b,c) water-soluble products 21b and solid precipitates
tla from the reaction of fullerenols with &I. HCl(0.4 M ) at 80 "C;(d) recovered fullerenols
from the treatment of 21a and 21b with aqueous NaOH
104
the remaining solution was dried in vaccum at 50 "C to give solid products 21b. W
spectra of both 21a and 21b showed a new pronounced carbonyl absorption band at
1722 cm-1 and the retention of five characteristic hllerenol absorptions at 3424, 1595,
1392, 1084, and 593 cm-1, the intensities differing fiom that of the initial hllerenol (Fig.
19a). The observed carbonyl absorption confirmed the ketone presence in 21. The
spectra indicated that the chemical structures of 21a and 21b are related to each other,
presumably in having a different degree of hemiketal to ketone conversion. The driving
force for this facile acid-catalyzed conversion is the stabilization, by an oxygen atom, of a
tertiary alkyl carbocation derived from the protonation of the hemiketal hnction in 20,
and the elimination of a hydroxy proton to give the corresponding ketone. Interestingly,
brown solids are precipitated by treatment of 21a or 2lb with aqueous alkaline solution
(2M NaOH). After the removal of NaOH by repeated washing with water and methanol,
these brown solids exhibited a nearly identical IR spectrum (Fig. 19d) to that of the
starting fbllerenols. This pH-dependent reversible interconversion of hemiketal and
ketone, clearly excludes the alternative Pinacol rearrangement. To further support the
existence of hemiketal structures in hllerenols 1, an ethylation reaction was performed
with triethyloxonium tetrafluoroborate (Et30+-BFq-) in I , 1,2-trichloroethane at 85 "C
in order to attack the ketal moiety The reaction converted the hemiketal groups, through
ring opening, to the corresponding ethoxy and ketone structures. As expected, a
carbonyl absorption band at 1726 cm-l was observed in the IR spectrum of the products,
indicating ketone formation during the reaction, consistent with the above structural
hypothesis.
In summary, the chemical structure of hllerenols 1 was shown to consist of
hemiketal moieties as well as tertiary hydroxy groups. This interesting observation of
hemiketal functions on the fullerene skeleton requires in turn, postulation of a
hypothetical mechanism involving hydroxylated fullerene oxide as one of the reaction
intermediates. Treatment of hllerenol 3,which lacks hemiketal moieties, with dilute HCI
(2M) at ambient temperature, gave products showing a nearly identical IR spectrum to
that of the starting material, and no carbonyl absorptions. Moreover, the lack of carbon
peaks in the region of 6 160-175 (corresponding to the chemical shift of vinyl ether
carbons) in Fig. 1 Ic and 1 Id, strongly suggested the exclusion of hemiketal moieties in
fUllerenol3. That differentiates the chemical structure of 3 fiom 1.
105
References
1. The first theoretical prediction: Z. Yoshida and E. Osawa, Kugakudojin, Kyoto (1971) 174.
2. For overviews of fullerene preparation and properties see: H. W. Kroto, A. W. Allaf, and S.
P. Balm,Chem. Rev. 91 (1991) 1213 and references therein.
3. A. F. Hebard, M. J. Rosseinsky, R. C. Haddon, D. W. Murphy, S. H. Glarum, T.T. M.
Palstra. A. P. Ramirez and A. R. Kortan, Nature 350 (1991) 600.
4. R. C . Haddon. Acc. Chem. Res. 25 (1992) 127.
5 . K. Tanigaki, T.W. Ebbesen, S. Saito, J. Mizuki, J. S. Tsai, Y. Kubo and S. Kuroshima,
Nature 352 (1991) 222.
6. For review of fullerene chemistry see: R. Taylor and D. R. M. Walton, Nature 363 (1993)
685.
7. R. D. Johnson, G. Meijer and D. S . Bethune, J. Am. Chem. SOC.112 (1990) 8983.
8. P. M.Allemand, K. C. Khemani, A. Koch, F. Wudl, K. Holczer, S. Donovan, G. Gnmer,
J. D. Thompson, Science 253 (1991) 301.
9. Y . Wang, f. Chern. Phys. 96 (1992) 764.
10. N. S.Saricifti, L. Smilowitz, A. J. Heeger and F. Wudl, Science 258 (1992) 1474.
11. C. S. Kuo, F. G. Wakim, S. K. Sengupta and S . K. Tripathy, Solid State commun. 87
(1993) 115.
12. K. Chen, W. B. Caldwell and C. A. Mirkin, J. Am. Chem. Soc. 115 (1993) 1193.
13. W. B. Calwell, K. Chen, C. A. Mirkin and S. J. Babinec, Langmuir 9 (1993) 1945.
14. J. A. Chupa. S. Xu, R. F. Fischetti. R. M. Strongin, J. P. McCauley, A. B. Smith,
J. K. Blasie, L. J. Peticolas and J. C. Bean, J. Am. Chem. Soc. 1993, 115, 4383.
15. K. L. Wooley, C. J. Hawker, J. M. J. Frechet, F. Wudl, G. Srdanov, S. Shi, C. Li
and M. Kao, J. Am. Chem. SOC.115 (1993) 9836.
16. R. E.Haufler, J. Conceicao, L. P. F. Chibante, Y. Chai, N. E. Byrne, S. Flanagan,
M. M. Haley, S. C. OBrien, C. Pan, Z. Xiao, W. E. Billups, M. A. Ciufolini, R. H.
Hauge, J. L. Margrave, L. J. Wilson, R. F.Curl and R. E. Smalley, J. Phys. Chem.
94 (1990) 8634.
17. P. M. Allemand, A. Koch, F. Wudl, Y. Rubin, F. Diederich. M. M. Alvarez, S. J.
Anz and R. L. Whetten, J. Am. Chem. SOC. 113 (1991) 1050.
18. D. M. Cox, S. Bahal, M. Disko, S. M. Gorun, M. Greaney, C. S. Hsu, E. B.
Kollin, J. Millar, J. Robbins, R. D. Shenvood and P. Tindall, J. Am. Chem. SOC.
113 (1991) 2940.
106
19. C. Jehoulet, A. J. Bard and F. Wudl, J. Am. Chem. SOC.113 (1991) 5456.
20. D. Dubois, K. M. Kadish, S. Flanagan, R. E. Haufler, L. P. Chibante and L. J.
Wilson, J. Am. Chem. SOC.113 (1991) 4364.
21. D. Dubois, K. M. Kadish, S. Flanagan and L. J. Wilson, J . Am. Chem. SOC.113
(1991) 7773.
22. Q. Xie, E. Perez-Corder0 and L. Echegoyen, J. Am. Chem. SOC.114 (1992) 3978.
23. Q. Xie, F. Arias and L. Echegoyen, J. Am. Chem. SOC. 115 (1993) 9818.
24. D. L. Lichtenberger, K. W. Nebesny, C. D. Ray, D. R. Huffman and L. D. Lamb,
Chem. Phys. Lett. 176 (1991) 203.
25. F. Wudl, A. Hirsch, K. Khemani, T. Suzuki, P. M.Allemand, A. Koch, H. Eckert,
G . Srdanov and H. Webb, ACS Symp. Ser. 481 (1992) 161.
26. A. Hirsch, Q. Li and F. Wudl, Angew. Chem., Int. Ed. Engl. 30 (1991) 1309.
27. A. Hirsch, A. Soi and H. R. Karfunkel, Angew. Chem., Int. Ed. Engl.. 31 (1992)
766.
28. S. G. Kukolich and D. R. Huffman, Chem. Phys. Lett. 182 (1991) 263.
29. H. Thomann, M. Bernardo and G. P. Miller, J. Am. Chem. SOC.114 (1992) 6593.
30. G. P. Miller, C. S. Hsu, H. Thomann, L. Y. Chiang and M. Bernardo, Mat. Res.
Symp. Proc. 247 (1992) 293.
31. H. Selig, C. Lifshitz, T. Peres, J. E. Fischer, A. R. McGhie, W. J. Romanoq. J. P.
McCauley Jr. and A. B. Smith, J. Am. Chem. SOC.113 (1991) 5475.
32. J. H. Holloway, E. G. Hope, R. Taylor, G. J. Langley, A. G. Avent, J. T. Dennis,
J. P. Hare, H. W. Kroto and D. R. M. Walton, J. Chem. SOC.,Chem. Cornmun.
(1991) 9666.
33. P. R. Birkett, P. W. Hitchcock, H. W. Kroto, R. Taylor and D. R. M. Walton,
Nature 357 (1992) 479.
34. F. N. Tebbe, R. L. Harlow, D. B. Chase, D. L. Thorn, G. C. Campbell, J. C.
Calabrese, N. Herron, R. J. Young and E. Wasserrnan, Science 256 (1992) 822.
35. G. A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Sensharma, G.
K. S. Prakash, 1. Am. Chem. SOC.113 (1991) 9385.
36. F. N. Tebbe, J. Y. Becker, D. B. Chase, L. E. Firment, E. R. Holler, B. S. Malone,
P. J. Krusic and E. Wasserman, J. Am. Chem. SOC.113 (1991) 9900.
37. G. A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Sensharma. G.
K. S. Prakash, J. Am. Chem. SOC.113 (1991) 9387.
107
Fluorination
1. Introduction
109
110
2. Theoretical Considerations
There was initial disagreement amongst theoreticians as to whether C&so
should occur. Whilst ab initio Hartree-Fock calculations using a double-zeta plus potential
'
@ZP) method suggested that it should,l4 a similar independent study produced a more
sceptical conclusion, namely, that perfluoro [60]hllerene 'may not be easily isolable'. *
However, both agreed that steric interactions between adjacent fluorines would result in
lengthening of the C-C bonds in the [60] hllerene cage to 1.672 A. Independent
calculations employing density function methods have predicted a 15% weakening of the
C-Fbonds compared with those in CF4 but suggest stability for C6oF60 l6 while others
have indicated that twisting of the carbon skeleton can partially reduce the strain but retain
I symmetry.17
A series of papers18319920 using semi-empirical calculations have demonstrated
that [60]hllerene is susceptible to equimolar X2 addition of H, F, CI, Br and I, forming
the 1,2 and 1,4-additions analogous to the addition to the ethene and butadiene moieties
respectively. In considering the electronic structures of 1,2- and 1,4- added C6#2n1s (n =
1, 2, 4, 6, 8, 10, 12, 18, 14 and 30) the reaction C6o + nF2 -+ is exothermic.
The exothermicity in the fluorine case is lower than that for the other halogens. A larger
destabilization as n increases is predicted for 1,Zaddition whereas this is not the case for
1,Caddition up to n = 12. The destabilization for 1,Z-addition begins at ca. n = 8 and
111
originate8 &om the interaction of substituents which are added at adjacent double bonds
in [6O]lllerene. Preference for 1,Zaddition for F should occur at n < 8.20 Similar
calculations by an independent group have confirmed that the favoured isomers involve
1,2- and 1,4-additions with higher energy ones resulting from 1,6- and 48-additions.
Consideration of isomers represented by 1,3-, 1,5- and 1,7-additions have led to the
conclusion that these are only stable in the case of fluorine addition.2l
Pluoro[60]Mlerene has been used as an example to confirm that steric22 and
n-electrOnic factors23 are major influences on the stability of regioisomers of oxidized
fillerones and, more recently, the energetics and geometries of the local structures of
both Q @ X o and C 6 o X e d , and C7oX clusters have been studied. This has led to the
conclusion that a structure having even one C-F endohedral bond is less stable and that
the differdnce in energy between C60Fendo and c60Fex0 clusters is 223 kl mol-1 . The
study has also produced data indicating four stable isomers for C7oF.24
3. Preparations
3.1 Fluorination of C60 and C6OK70 Mixtures
Since only 24 groups can be attached to a spherical [6O]fillerene cage without
being dacent, for many molecular groupings this is the maximum number of groups that
will be linked to the fillerene cage. Such is the case when CH3 groups11 or large single
atoms like chl0rin6~9~7 or b r o m i n e l 3 ~are
~ ~attached. When smaller atoms such as
hydrogen are used, larger numbers of attachments can be anticipated. Indeed,
hydrogenation is rather easy but the products are difficult to characterize definitively and
mass spectrometry indicates only the partially hydrogenated species C6$-2,29C&18
and w 3 6 , 3 0 all of which are unstable. Fluorine is also small and forms rather strong
bonds with most other elements including carbon. Studies in which [60]fillerene was
expored to elemental fluorine have shown that, unlike the hydrogen case, comprehensive
ad- takes place although the extent depends on experimental ~onditions.7~3~ Direct
fluoriMion of pure [6O]fUerene to saturation at about 70 OC is slow and mass
spectrometric data on the partially fluorinated products suggested particular stability for
intermuiiates of composition c6$6 and c6@42. A 1% NMR spectrum ofthe ultimate
off-white product after 12 days exposure exhibited a singlet at -150.5 and/or 153 ppm
supQimposed upon a double-humped background, the humps being centred at
approximately -144.4 and -158.0 ppm, in addition to a peak at -188.5 ppm indicative of
the prsrrence of IF. It was suggested that the singlet might be due to C&6o but that
112
other symmetrical species c6@6, c6OF12 or c6@20 could also be responsible for the
spectnun.31 Subsequently, this singlet has been observed independently by other
researchers and attributed to a highly-symmetric fluorofbllerene other than C60F60*32
and l% solid state NMR spectra on the products of the fluorination of C6o and
C6dc70 mixtures have been shown to exhibit one broad line centred at -70
ppm//CF3COOH which, again, coincides with the values found in the solution studies
(i.e. -70 + -78 = -148 ~ p m ) . ~Very
3 recently, the I9F NMR spectrum of the product of
the fluorination of [60]hllerene with KrF2 has been found to be similar to that of the
products of direct fluorination and, in particular, shows the sharp singlet at -151 ~ p r n . ~
The earliest study on the fluorination of fbllerenes was carried out on C60/C70
mixtures at room temperature.7 The reactions occur much more rapidly than in the
[60]fhllerene case,31 probably because of the facile fluorination of [70]hllerene which is
usually complete within a few minutes (see Section 3.3). Results varied, but fluorine
uptake was estimated to yield products with F:C60 ratio >30 whilst fluorination of one
sample of pure [60]fbllerene gave a weight increase corresponding to a ratio of 38.7 It is
clear from mass spectrometric measurements of these products that C6oF36 has a
particular stability which compares with that of the product of reduction, c6@36, in
which it has been postulated that the stability derives from the formation of four highly
delocalised benzenoid rings.3o Evidence of compounds with higher fluorine content in
which the number of fluorines is always an even number (c6oF38 -k -+ c6@52+) were
also apparent.7 The most intense peak in the products of fluorination of 70]fUllerene
corresponded to that Of C7@40+ and masses attributable to higher fluorination products
up to C7@46+ were also found7
Room-temperature fluorination by the same group using pure [60]fullerene32
has confirmed much of the earlier work?i namely that the fluorination process is slow, a
major peak in the mass spectrum is associated with c6oF42, and a sharp peak is
observed at -149 ppm in the 1% NMR spectrum as well as the singlet associated with
HF. In addition, the presence of traces of C6@60 in unsublimed products was also
detected. However, the infrared spectra associated with the final products of fluorination
from the two groups differ 31,32 In one case31 a strong broad C-F stretching band at
1148 cm-1, prominent in the products of initial fluorination, diminished with hrther
fluorination to yield sharp bands at 1060 and 1035 cm-l, and bands at 1067 and 1027
cm-1 were correlated with the species giving rise to the l% NMR signal at -150.5 ppm.
In the second,32 a strong broad absorption at 1165 cm-1 associated with the C-F
stretching vibration was observed, which shies to lower frequency 0s fluorine uptake
113
increased. The lowest frequency band observed was 1130 cm-l which is ca. 100 cm-l
higher than the towest frequency observed by the first group.
Efforts to synthesize filly fluorinated [60]fillerene in high yield have continued.
Attempts in which extreme physical conditions have been applied have resulted in the
break-up of the [60]hllerene sphere with the production of perfluoronaphthalene and
perfl~orodecalin.3~ The use of the halogen fluorides, ClF3, BrF5 and IF7 have shown
that IF7 does not react in the gaseous state while ClF3 and BrF5 act as both
halogenofluorhating agents as well as fluorinating agents. However, the number of
halogen atoms in the products are lower than with fluorine alone, possibly because of
stereoohemical hindrance. The products also contain significant quantities of oxygen-
containiq species.2
Krypton difluoride is a more powerful low-temperature fluorinating agent than
fluorine itself and should offer one of the best possibilities of producing perfluoro[60]-
fUllerene. However,mass spectrometry of the white product shows the most abundant
specisr to be C6oF46. Cage-opened species up to c6oF78 are also present.4 This
result is clearly similar to those obtained by the firther fluorination of a fluorohllerene
with simultaneousU.V. radiation3 (see below and Section 3.2).
It is now established that duect fluorination of [60]hllerene with elemental
fluorine gives a variety of species up to C6oF60 but no single compounds have been
Conolusively characterized and isolated. It is also evident that the nature of the
[6O]fullc#ene affects the product. Some samples undergo surface fluorination such that
unrG(Lctdd [6O]lllerene remains in the product. Although it has been suggested recently
that fwlerenes containing only a few fluorines can exist other than as products of mass-
spectrometric decomposition6 the only experimental evidence of such species has come
from e.p.r, examination of CdSF5Cl mixtures in ten-butylbenzene or toluene which
indicated the presence of C6oF formed presumably from decomposition of unstable
6&Fj (f.e. C60SF5 + SF4 +
So far, chloro- and bromo-fbllerenes have proved to be too unstable to yield
mass spectra but the fluorofillerenes have been successfidly extensively studied 1-395~7~8
For axample, the products of fluorination of the C6o and C60/70 (ca.9: 1) mixtures with
fluorindhelium mixtures at different temperatures have been studied by both positive and
negative ion mass spectrometric techniques. Although no pertluoro-derivatives were
detected species of composition C6& and C70Fy x 5 48; y S 56 respectively, were
o b m e d . In spite of the application of a range of different ionisation methods, and in
partiaular the fact that neither plasma-desorption negative ion time-of-flight mass
114
ss RR
decrease in ion intensity above c6oF48. In one case this has been attributed to the more
highly fluorinated species being cage opened,4 but in the other, comparison of the
fragmentation products with those from the products of simple direct fluorination have
shown a greater preponderance of odd-mass species on hyperfluorination, and has been
taken to be indicative of closed-cage species being the origin. The argument is that an
important pathway for decomposition involves loss of CF3 8s12 as well as F and CF2;12
an open-cage entity must have CF2 groups present initially which may be lost
preferentially thus retaining an even mass, but a closed-cage species will always have an
even number of fluorines present as C-F, and loss of F or CF3 followed by CFz will give
rise to odd-mass fiagmentation.4
Little is Mitten about oxygen-containing species in the products of the U.V.
fluorination of (2603 but it is evident in the KrF2-fluorinated products, despite exposure of
the samples to air prior to analysis, oxygen derivatives are in only low concentration. This
implies that the oxides are not a result of atmospheric oxidation. The possibility that
oxygen incorporation may be dependent on the fluorination method3 may be correct; for
example, oxygen contamination of the fluorine itself could be the origin. Krypton
difluoride will be free of such impurity. However, the fact that the action of methanol with
the product gave little change in the mass spectrum is surprising. The reason may be that
the hypduorinated material, being largely cage opened, lessens the driving force for
nucleophilic substitution which is so marked in the C6oF, (x I60) species4 It is also
noteworthy that the NMR spectrum of the product of KrF2 fluorination in THF
solution is similar to that found with the products of fluorination by elemental f l ~ o r i n e . ~
is C7oF385 which again differs from the C7#407 and C70F52~species which are
detected in the products emanating from fluorination of mixtures.
The 19F NMR spectrum of the products of fluorination of [7O]fullerene exhibits
-
singlets at -152.36 and -153.03 ppm (intensity ratio 2: 1) with smaller singlets at -151.2,
151.79, and -153.65 ppm, However, there is little evidence for the broad background
hump which is associated with the spectrum of the products of fluorination of
[6O]tirllerene.5 The singlets have been assumed to indicate the presence of one or more
products of high symmetry. The infrared spectrum of the product, deposited on a KBr
window fiom THF solution, exhibits a broad peak at 11 12 cm-1 associated with a C-F
stretching band, along with weaker bands attributable to C=O, OH and C-H which may
be due to occluded solvent. Warming of the sample at 80 "C under vacuum, however,
failed to remove these.
Holloway, E.G. Hope and G.J. Langley, Nature, 355 (1992) 27.
12. R. Taylor, G.J. Langley, A.K. Brisdon, J.H. Holloway, E.G. Hope, H.W. Kroto and
D.R.M. Walton, J. Chem. Soc., Chem. Commun.,(1993) 875.
13. P.R. Birkett, P.B. Hitchcock, H.W. Kroto, R. Taylor and D.R.M. Walton, Nurure,
357 (1992) 479.
14. G.E. Scuseria, Chem. Phys. Left., 176 (1991) 423.
15. J. Cioslowski, Chem. Phys. Left.,181 (1991) 68.
16. B.I. Dunlap, D.W. Brenner, J.W. Mintmire, R.C. Mowrey and C.T. White, J. Phys.
Chem.,95 (1991) 5763.
17. P.W. Fowler, H.W. Kroto, R. Taylor and D.R.M. Walton, J. Chem. SOC.,Fmaday
Truns.,87 (1991) 2685.
18. D.A. Dixon, N. Matsuzawa, T. Fukunaga and FN. Tebbe, J. Phys. Chem., 96 (1992)
6107.
19. N. Matsuzawa, D.A. Dixon and P.J. Krusic, J. Phys. Chem., 96 (1992) 83 17.
20. N. Matsuzawa, T. Fukunaga and D.A. Dixon, J. Phys. Chem.,96 (1992) 10747.
21. J.B. Peel and R.G. Rothwell, Australian. J. Chem., 47 (1994) 131.
22. P.N. D'yachkov, N.N. Breslavskaya and E.G. Ippolitov, Dokl. A M . Nauk, 331 (1993)
315.
23. P.N. D'yachkov, N.N. Breslavskaya and E.G. Ippolitov, Dokf.A W . Nauk, 334 (1994)
33.
24. N.N. Breslavskaya and P.N. D'yachkov, Koord. Khimiya, 20 (1994) 803.
25. J.W. Bausch, G.K.S.Prakash and G.A. Olah, J. Am. Chem. Soc.,113 (1992) 3205.
26. F.N. Tebbe, J.Y. Becker, D.C. Chase, L.E. Firment, E.R. Holler, B.S. Malone, P.J.
Krusic and E. Wasserman, J. Am. Chem. Soc.,113 (1991) 9900.
27. G.A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N.J. Trivedi, D.K. Sensharma and
G.K.S. Prakash, J. Am. Chem. SOC.,113 (1991) 9385.
28. F.N. Tebbe, R.L. Harlow, D.B. Chase, D.L. Thorn, G.C.Campbell, J.C. Calabrese,
N. Herron, R.J. Young and E. Wasserman, Science, 2% (1992) 822.
29. C.C. Henderson and P.A. Cahill, Science, 259 (1993) 1885.
30. R. Taylor, J. Chem. Soc., Perkin Trans.2 (1993) 1667; Philos. Trans, R. Soc.
London A 343 (1993) 87
3 1. Holloway, E.G. Hope, R.Taylor, G.J. Langley, A.G. Avent, T.J. Dennis, J.P. Hare,
H.W. Kroto and D.R.M. Walton, J. Chem. SOC.,Chem. Commun.,(1991) 966.
32. K. Kniaz, J.E. Fischer, H. Selig, G.B.M. Vaughan, W.J. Romanov, D.M. Cox, S.K.
Chowdhury, J.P. McCauley, R.M. Strongin and A.B. Smith, J. Am. Chem. Soc., 115
121
(1993) 6060.
33.H.HamWi, C. Fabre, P. Chaurand, S. Della-Negra, C. Ciot, D. Djurado, J. Dupuis
and A. Rassat, Fuiierene Science and Technoiogv, 1 (1993)499.
34.S a R.N. Compton e? ul., Ref.18 in H. Selig, K. Kniaz, G.B.M. Vaughan, J.E.
Fischer and A.B. Smith, Macromol. Symp., 82 (1994)89.
35.J.R. Morton, K.F. Preston and F. Negri, Chem. Phys. Lett., 221 (1994)59.
36.A.A. Gakh, A.A. Tuinman, J.L. Adcock, R.A. Sachleben and R.N. Compton, J. Am.
Ckm.Soc.,116 (1994)819.
37.P.J. Benning, T.R. Ohno, J.H. Weaver, P. Mukherjee, J.L. Adcock, R.N. Compton
aadB.1.Dunlap, Phys. Rev. B, 47 (1993)1589.
38.T. Nakajima and Y. Matsuo, Carbon, 30 (1992) 1 1 19.
39.D.M. Cox, S.D. Cameron, A. Tuinman, A. Gakh, J.L. Adcock, R.N. Compton, E.W.
Hagaman, K. Kniaz, J.E. Fischer, R.M. Strongin, M.A. Cichy and A. Smith, J. Am.
Chem. Soc., 116(1994) 1115.
40.F.Okino, H. Touhara, K. Seki, R. Mitsumoto, K. Shigematsu and Y. Achiba,
Fulierene Sci. and Tech., 1 (1993)425.
41.F.Okino, private communication.
42.Comments attributed to A.A. Gakh in Chem. & Eng. News, July 5 (1993)19.
43.R.Taylor and D.R.M. Walton, Nature, 363 (1993)685.
44.P.R.Birkett, unpublished results.
45.H,W. Kroto, J.R. Heath, S.C. OBrien, R. F. Curl and R.E. Smdey, Nuture, 318
(1985)162.
46.A.W. Allaf, S.P. Balm, R.A. Hdett, K.G. McKay and H.W. Kroto, Proc. Indian
A d Sci. (Chem. Sci.), 103 (1991)517.
47.J.M. Wood, B. Kahr, S.H. Hoke, L. Dejarme, R.G. Cooks and D. Ben-Amotz, J.
Am. Chem. Soc.,113 (1991)5907.
48.K.M.Creegan, J.L. Robbins, W.K. Robbm, J.M. Millar, R.D. Sherwood, P.J.
TinW and D.M. Cox, J. Am. Chem. SOC.,114 (1992) 1103.
49.W.A. Kalsbeck and H.W. Thorp,J Electround. Chem., 314 (1991)363.
50. F. Diderich, R. Ettl, Y.Rubin, R.L. Wheeton, R. Beck, M. Alvarez, D. Shensharma,
F. Wudl, K.C. Khemani and A. Koch, Science, 252 (1991)548.
51.R. Taylor, J.H. Holloway, E.G. Hope, G.J. Langley, A.G. Avent, T.J. Dennis, J.P.
Hare, H.W. Kroto and D.R.M. Walton, Nature, 355 (1992)27.
52.G.P.Miller, C.S. Hsu, H. Thomann, L.Y. Chiang and M. Bernado, Mu?er.Res. SOC.
Symp. Proc., 247 (1 992)293.
122
53. A.K. Brisdon, J.H. Holloway and E.G. Hope, unpublished work.
54. P.J.Fagan, P.J. Krusic, C.N. McEwan, J. Lazar,D. Holrnes Parker, N. Herron and
E. Wasserman, Science, 262 (1993) 404.
55. A.A. Gakh, A.A. Tuinman, J.L.Adcock and R.N. Cornpton, Tetrahedron Lett., 34
(1993) 7167.
Chapter 7
Roger Taylor
123
124
1. Iodination
Iodination of hllerenes has not been achieved. This is not surprising in view of
the relative stabilities of halogenohllerenes compared to halogeno-organics in general,
and the tendency of both iodoalkanes and iodoarenes to e l i n a t e iodine. Thus although
no derivative with fbllerene-iodine bonding has been prepared (nor seems likely to be)
intercalation of iodine into the fbllerene lattice has been a~hieved.l-~ For example,
heating [60]hllerene with up to twelve equivalents of iodine under vacuum at 250 "C
produced a product of approximate stoicheiometry C60.212 with iodine molecules
intercalated into a face centred cubic array of [60]hllerene molecules, each llierene
layer consisting of a simple hexagonal lattice.1 A similar experiment carried out at
130 "C using a large excess of iodine showed no reaction to occur during 20 h.
However, W irradiation (Hg lamp) under the same conditions produced a product of
approximate stoicheiometry C60.12. X-ray diffraction studies showed that the close-
packed face-centred cubic structure of [60]hllerene is retained, with iodine atoms
inserted between the hexagonal basal planes, producing increased spacing between the
layers5 These intercalates slowly lose iodine upon standing, and tested down to 4 K,
none of them show superconductingproperties. This may not be too surprising, given
that iodine is an x-electron acceptor and [60]hllerene is highly electrophilic.
2. Bromiortion
Bromination of [60]fillerene by neat bromine at 20-50 "C was reported initially
to result in the uptake of between two and four bromine atoms7 (based on weight
uptake). Although this was subsequently found to be incorrect, the bromofillerene
product was found to be thermally decomposed (at 150 "C) back into [60]fillerene, and
to do so under mass spectrometric conditions. Therein lies one of the problems attendant
upon research in this (and indeed many other lllerene areas), naqely the inability to
detect the products by mass spectrometry. Circumstantial evidence can be obtained by
replacing the bromines by other, less thermally labile groups, but this turns out to be
difficult too because the bromo derivativestend to be very insoluble. This also rules out
the use of 1% except solid state, though this latter has been precluded at present
by the small amounts of material available.
More recent studies9.10 showed that bromination of [60]fillerene with neat
bromine produces a yellow-orange microcrystalline derivative having the approximate
stoicheiometric composition C60Br25-2g. Since twenty-eight bromines cannot be
attached to [60]fillerene in a symmetrical way, this suggested (especially in view of the
intercalation of iodine) that the derivative was in fact C60Br24 with additional bromine
trapped in the interstices of the crystals. This was confirmed by single crystal X-ray
studies9 which revealed the Th structure shown in Fig. 2; the corresponding Schlegel
diagram is shown in Fig. 3. The high symmetry of this derivative is evident in the
simplicity of the IR spectrum (Fig. 4a).9 The particular sample of the derivativethat was
used for the X-ray structure contained approximately one molecule of bromine for each
C6oBr24 molecule, but with a disordered c o r ~ f i g u r a t i o n The
. ~ ~ ~structure
~ of this
derivative can be envisaged as consisting either of twelve hexagons, each with a 1,4-
arrangement of two bromine atoms (in a boat conformation), or of eight hexagons each
with a 1,3,5-arrangement of three bromine atoms (in a chair conformation).Although the
126
molecule has a double bond in each pentagonal ring, these latter also contain two $-
hybridised carbon atoms which thereby diminishes the strain that would otherwise
resu1t.R studies indicated that at any time during heating at 150 "C for 24 h, the product
consisted of [60]Werene and undecomposed C6oBr24, suggestingthat the bromine loss
is a cascade process.11
The W A C name for C60Br24 is 1,4,7,10,12,14,16,19,22,24,27,29,31,33,36,-
38,41,43,46,49,52,54,57,60tetracosabromo-1,4,7,10,12,14,16,19,22,24,27,29,31,33,36,
38,41,43,46,49,52,54,57,60-tetraco~ydro-[6O]lllerene,the second half of the name
being necessary simply because 'bromo' is a replacement term, and therefore is regarded
as having replaced hydrogens (even though these were not there in the 6rst place). It
would be unrealistic to imagine that practising lllerene chemists will not dispense with
the second half of the name in general discussion and description at the very least. It is
perhaps fortunate therefore that c60Bf24 is so insoluble that it may not feature much in
lllcrene chemistry.
Bromination of [70]lllerene under the same conditions also gives a product of
approximatecomposition C70Br28, but the structure is not known.11 It may be relevant
ther&re that C7oBr24 is predicted to be the product of highest addition level.12 The
bromo adduct decomposes on heating in the manner of the [60]lllerene derivative.11
Brotnination of [60]lllerene by bromine in either carbon disulfide or chloroform
gives dark brown prisms of C6gBrg in 80 and 58% yields, respectively. The structure,
determined by single crystal X-ray diffraction is shown in Fig. 5 , and the dispositions of
the bromines is also encircled in the Schlegel diagram in Fig. 3. There are many ways in
which the Brg pattern can be fitted into the Br24 pattern, because in both C60Br24 and
C6gBrg, the relative configurationsof the bromines is the same. (NB. The set in Fig. 5
of ref. 11 has been outlined inCOKeCtly, but is shown correctly in Fig. 19 of ref. 13.). It is
probable therefore that C(jgBr8 is an intermediate on the pathway to formation of
C6oBr24. From inspection of Fig. 3 one can anticipate that there may be other stable
intermediates in which the integrity of the Bt-8 pattern is maintained, such as C6@14
and C6oBr20 but none have so far been isolated.
As in the case of C6oBr24, molecules of bromine are occluded in the C@r8
lattice, in this case two molecules for each molecule of C@rg, and the bromine is
partially ordered. Fig. 6 shows the channels parallel to the c-axis, into which the bromine
molecules fit.
On heating, C6gBrg loses bromine and does so more readily than C6@r24 This
relative stability can be attributed to the lower bond reorganisationneeded to re-acquire
128
Figure 5 Crystal structure for c6OBrg Figure 6 Crystal structure OfC6@rf~showing the
channels into which the bromines fit
Q
129
Figurn 9 Possible mode of rearrangement of W r 6 into C&g, initiated by the 1,2-bromo eclipsing
interaction,followed by addition of lattice-occludedbromine
along the pathway to C60Br6 it cannot be stabilised and therefore necessarily acquires an
additional bromine, even though this results in unfavourable 1,2-eclipsing interactions.
The stabilities of the brominated [60]fbllerenes have also been calculated by the
AM1 method which indicates that some C6gBr4, C60Br10, C60Eirl2, and C6@r18
derivatives should also be isolable. *
3. Chlorination
There is every indication that chlorination is Likely to be, at least in the short term,
the most important of the halogenation reactions of hllerenes. Success has already been
achieved in controlling the addition in the manner of bromination, but with the all-
important benefit of solubility of the derivatives.
An early report of chlorination of a mixture of (601-and [70]&llerene by chlorine
gas at 250 "C indicated the uptake of twenty-four chlorine atoms per molecule of
fbllerene mixture, giving a light orange product, soluble in many organic solvents.7 No
mass spectrum could be obtained because of the ease with which the chlorine is lost, and
separate experiments showed that under argon at 400 "C all the chlorine is lost. This is
however a higher temperature than that needed for debromination and demonstrates the
higher stability of the chloro derivatives. Other workers reported that the reaction of
liquid chlorine at cu. -35 O C with [60]&1lerene produced a brown solid of approximate
composition C6oC112 and that this dechiorinated on heating 200-350 OC.1O This thus
shows a parallel with the results for the bromo compounds, whereby the derivative with
the higher degree of addition is the more stable one. No stmctural characterisationof the
compound was possible, and a mixture of product may have been formed. Nevertheless.
in view of the results described below it seems quite probable that a major component
has two sets of six chlorines arranged around polar pentagons, in the manner found for
CLAClL Chdnwl
131
w
148.4 148.2 1480 147.8 147.61147.4 147.2 147.0 148.8 148.6 146.4 146.2
6
I I
80 70 60
6
Figure 12 Part of the 13C N M R spectrum for C60Cl6, and the proposed structure
133
References
1. Q. Zhu, D. E. Cox, J. E. Fischer, K. Kniaz, A. R McGhie, and 0.Zhou, Nafure,355
(1992) 712.
2. M. Kobayashi, Y. Akahama, H. Kawamura, H. Shinohara, H. Sato, and Y . Saito,
Solid Stale Commun.,81 (1 992) 93.
3. Y. Maniwa, T. Shibata, K. Mizoguchi, K. Kume, K. Kikuchi, I. Ikemoto, S. Suzuki,
and Y. Achiba, J. Phys. Soc.Jpn., 61 (1992) 22 12
4. 0.Zhou and D. E. Cox, J. Phys. Chem. Soliak, 53 (1992) 1373.
5. T. Zenner and H. Zabel, J. Phys. Chem., 97 (I 993) 8690.
6. P. R. Birkett, C. Christides, P. B. Hitchcock, H. W. Kroto, K.Prassides, R. Taylor,
and D. R. M. Walton, J. Chem. Soc.,Perkin Trans. 2, (1993) 1407.
7. G. A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. P.Trivedi, D. K. Sensharma, and
G. K. S . Prakash, J. Am. Chem. Soc., 113 (1991) 9385.
8. R. C. Haddon, Acc. Chem. Res., 25 (1992) 127.
9. F. N. Tebbe, R. L. Harlow, D. B. Chase, D. L. Thorn, G. C. Campbell, J. C.
Calabrese, N. Herron, R. J. Young, and E. Wassennan, Science, 256 (1992) 822.
10. F. N. Tebbe, J. Y.Becker, D. B. Chase, L.E. Firment, E. R. Holler, B. S. Malone, P.
J. Krusic, and E. Wasserman, J. Am. Chem. SOC., 113 (1991) 9900.
11. P.R. Birkett, P. B. Hitchcock, H. W. Kroto, R. Taylor, and D. R. M. Walton,
Nature, 357 (1992) 479.
12. R. Taylor, J. Chem. Soc.,Perkin Trans 2., (1993) 8 13,
13. R,Taylor, Phil. Trans. R. SOC.Lo& A , 343 (1993) 87.
14. R. Taylor, Electrophilic Aromatic Substitution, (Wiley, Chichester, 1989), pp. 16-18.
15. J. B. Peel and R. G. Rothwell, Austr. J. Chem.,47 (1994) 13 1.
16. F. Cataldo, Carbon, 32 (1994) 437.
17. P. R. Birkett, A. G. Avent, A. D. Darwish, H. W. Kroto, R. Taylor, and D. R. M.
Wdton,J. Chem. Soc., Chem. Commun., (1993) 1230.
18. P. R. Birkett, A. D. Darwish, H. W. Kroto, R. Taylor, and D. R. M. Walton,
unpublished work.
19. P. R. Birkett, A. G. Avent, A. D. Darwish,H. W. Kroto, R. Taylor, and D. R. M.
Walton, J. Chem. Soc.,Chem. Commun., in press,
20. G. P.Miller, M. A. Buretea, J, W. Swircewski, and J M. Mcconnackie, unpublished
work (personal communication fiom G. P. Miller)
Chapter 8
Roger Taylor
There are various ways in which aryl groups may be attached to fbllerenes:
directly or by means of l i g atoms. Direct linkage may involve either a single bond
(arylation), or two bonds as a result of reaction with benzyne (arenylation). Linking
atoms may be carbon (see Chap. 9) and also in principle 0, S, or N, though no
derivativesof this type have yet been isolated and characterised.
In the context of this book, reactions are classified in terms of additions to
fbllerenes. However, the reactions of fullerenes with aryl groups f d also into one of the
most important and best known classes of organic reactions, namely electrophilic
aromatic substitutions. Fullerenes are very powefil electrophilesand are able to replace
the hydrogens in aromatics, the reactions falling thus into the general category of
alkylation by alkenes.1 This form of alkylation has been described asfullerenation,2 but
since saturation of the fullerene cage necessarily occurs across the addition site
filkrenylution is more consistent with standard nomenclature. Arylation may also be
accomplished by using fbllerene halides, and here reaction is faster because the
electropbilicity of the fullerene is increased..
135
136
spectrometry of the reaction products indicating the addition of up twelve and sixteen
aryl groups to the fUllerene.2 It was suggested that this process takes place via
protonation of the hllerene by residual protons in the aluminium chloride, giving a
fullerene cation, which as electrophile then attacks the aromatic ring. However, no
protonation of [6O]fullerene could be achieved with the superacid,
trifluoromethanesulphonicacid? and although PAICl4- (present in AICl3 that contains
traces of water) is a stronger super acid, reaction also takes place in the presence of
ferric chloride. A mechanism which involves direct coordination of the x-electrons of
the fUUerene with the Lewis acid seems more probable. Moreover, [60]fillerene in oleum
gives rise to radical cations,S so these may also be involved as electrophiles.
Sufficient information is can be gleaned from the above work and that of the
Sussex group for the following general conclusionsto be drawn:
1. The Lewis acid forms a complex with the fUllerene which then carries out
dkyiation of the aromatic.
2. The bulk of the fillerene is such that substitution at puru sites of the aromatic
will be favoured, probably exclusively.
3. The reactions follow the classic Lewis acid catalyst activation order i.e. AICl3
> FeCl3. For example, [60]fUllerene does not react with benzene in the presence of
FeCl3, but does so in the presence of AIC13.2
4. The reaction is faster with [60]fullerene than with [70]fullerene.2,6 This is
because [60]fUllerene is more electrophilic due to the greater strain in the molecule. This
greater electrophilicity shows up in other reactions e.g. the reaction with
cyclopentadiene,7 benzyne;6 reduction of [60]fullerene is also faster than that of
[701i~erene. 8
5. The reaction is faster with more reactive ar~matics.~ This needs to be taken
into account if hllerene soot is soxhlet-extracted with e.g. xylene, mesitylene etc. for
here there is the possibility that Lewis acid sites on the glass surface may act as the
catalysts, so degrading the quality of the extract (and also incidentally, giving
erroneously high extract yields).
A more detailed investigation of the reaction of [60]hllerene with bromine,
benzene and ferric chloride (in this case the products being subjected to normal work-up
procedures after heating under reflux for 24 h) showed (FAB mass spectrum) that a
number of products were ~ b t a i n e d Derivatives
.~ containing between five and twelve
phenyl groups attached to the cage were evident in the mass spectrum, the relative
intensities being: 2 : 11 ; 2 : 11 : 1 : 3 : 1 : 2. It is significant that peaks corresponding to
137
the species c6oph6 and C6oPh8 dominate in the spectrum in view of the results obtained
in bromination (see Chap. 7). Metastableion studies showed also that each peak contains
a contribution (at least) from fragmentation ions of higher phenylated species. Laser
desorption mass spectrometry also showed that species up to C6Ophl6 are present, and
that fragmmtationwith loss of a single phenyl group is a major process, so that species
in this caae containing odd numbers of phenyl groups tend to predominate. The presence
of oxygenated species were also detected for the first time, with up to two mygens being
attached to each [60]fhllerene molecule.
Further work involving HPLC separation of the products revealed the HPLC
trace shown in Fig. 1.10 At the time of writing this has not been fully analysed, but some
of the peaks have been characterised by EI mass spectrometry, and include C6Oph4
(Peak 7), C6@5H (Peak 81, C6$h5H3 (Pe* 9)s C6@k (Pe* lo), C6@h8 (Peak
Il), C6Ophl2 (peak 12), and C60Phl6 (tail material) together with some derivatives
containing up to two oxygens, or an oxygen and a methylene group, the latter believed to
be abstracted firom solvent during the work-up procedure. Figures 2-5 show the mass
Spectra for CfjflhgH, c6@&. C6@hl2, and C6@hSH3.
I 23 4-6 7 I 9 loll 12
IIIIII I I I II I
IntcnsiIy
20 40 60 80 tlmin-l
Figure 1 HPLC trace of the product of reaction of [dO]Nlerene with Br2, FeC13 and benzene
138
'I
','
1 I
3
191
1106
k+l$OO d o 0 d o 0 ld00
ml z
3.
Is.
a.
75.
n.
n.
a.
IS.
54.
6.
*.
35.
3).
18
mlZ
mlZ
Fipm S Mass of CmPh5H3
The structures of most of these derivatives is not yet known, and analysis of them
is an important goal in the search for the various addition patterns that [60]fUllerene is
capable of. It would be reasonable to suppose that the structure of C6oPk is similar to
140
that shown in Fig. 6 (the structure of which is discussed fbther below), but with X
replaced by a phenyl group, though preliminary evidence suggests that this may not be
the case, due to the steric constraints arising from two adjacent phenyl groups.l*
CrjoPh12 may then consist of two such assembliesof phenyl groups, but arranged around
diametrically opposed pentagons. However, it is also possible that an octahedral pattern
could be involved,12 though this is less probable in view of results which have been
40 A1
obtained on the fbrther chlorination and arylation of CmCb (see sect. 1.2). The
structure for C@b m y be related to that shown in Fig. 6, but without the aryl group
A and the group X.A plausible stmcture for the derivativeC60Ph5H02 is that shown in
Fig. 7, whwein addition takes place across the highly localised double bonds in the
p e n t a g d rings.
Though analysis of these products is a major exercise, it will provide a major
insight into the intermediates that are formed on bromination and their subsequent
substitution. It is not possible to determine the structures of these by mass spectrometry,
and t h y are also too insoluble for 13C NMR analysis. These difficulties are
circumvented in the phenyl derivatives which are more stable.
mixture with a spatula that has been used previously for dispensing ICI; if a clean spatula
is used then no reaction occurs.) With benzene the product is Cfj@hsCI, Fig. 4, X = CI,
and this gives the mass spectrum shown in Fig. 8, and is the first that has been obtained
for a lllerene with chlorine attached to the cage. Evidently, elimination of PhCl is
energetically less favourable than the elimination of CI2 that occurs so readily fiom
lllerenes possessing chlorine addends alone. The 13C NMR spectrum of this derivative
is similar to that shown in Fig. 12 of Chapter 7 in that there are twenty-eight peaks in the
& region of the spectrum (two peaks being of half intensity) and four peaks in the sp3-
region (peak height ratio, 1 : 1 : 2 : 2). This firmly supports the proposed structure. By
reaction with triphenylphosphine in the presence of traces of water, the chlorine is
replaced with hydrogen to give C60Ph5H., Fig. 6, X = H. l o Again a similar 13C TWR
spectrum is obtained, and the lH NMR spectrum shows a singlet at 6 5.2.
This technique has been used to prepare a range of aryl derivatives, the structures
of which have been confirmed by a variety of NMR methods.l* For example, the
reaction of C6oC16 with toluendfemc chloride followed by reaction with PPh3 gives
mainly C60(4-M&&)5H as shown by the mass spectrum in Fig. 9. Some C60(4-
M&&)6 is also produced together with traces of C60(4-MeCgH&, this latter being
obtained also from reaction of [60]lllerene with toluene and bromine in the presence of
1
111
9 0 1000 1100
143
ferric chloride, though here the main product seems to be C60(4-M&6&)4. Reaction
of C6oCk with fluorobenzendfemc chloride followed by reaction with PPh3 as above
gives C60(4-FC#&H, the product here appearing to be particularly susceptible to
oxidation to the di-epoxide c$. Fig. 7. Likewise the analogous reaction with t-butyl-
benzene produced mainly C60(4-t-BuC&)5Cl (and the hydrodechlorinated derivative),
thou@ again small amounts of products with six and seven aryl groups attached to the
cage were evident. Reaction also takes place readily with thiophene to give a product
with five 2-thiophenyl groups attached to the cage (the first heteroaromatic derivative of
a fullerone), but the product is particularly susceptibleto monooxidation.
Two-step procedures have also been used. Thus isolation of C60Ph~Cland then
reaction with benzene gave C&& the mass spectrum for which was effectively
identical to that in Fig. 3. Likewise, reaction with toluene gave C60Ph54-MePh (Fig.
10). If either [60]hUerene, or C60c16 are reacted with ICVCCb followed by reaction
with bemadferric chloride, then C6fJPhl2 is obtained, the mass spectrum being similar
to that shown in Fig. 4, except that the main component appears to be C6@hgHj, which
provides firm evidence that there are two groups of addends present each having the
general arrangement shown in Fig. 6. These are, for steric reasons, most probably on
opposite sides of the cage, in which case three different isomers are possible, i.e
accordingto whether equivalent groups are eclipsed or at angles of either 72' or 144' to
each other.
1
144
Since the C-Si bond is much more susceptible to cleavage by electrophiles than
the C-Hbond, then this would predict that alkyldesilylation would take place much more
readily than alkyldeprotonation.14 Surprisingly therefore, the reaction of
trimethylsilylbenzene, MqSiPh, with C6oCldferric chloride as above does not give the
expected alkyldesilylation, yielding phenyl groups attached to the cage. Instead,
substitution paru to the SiMe3 group occurs giving, after replacement of chlorine by
hydrogen, C60(4-SiMe3C&)5H, (Fig. 11) and it is probable that this is a result of
steric hindrance. This is an important result since cleavage of the SiMe3 groups by a
variety of electrophilesis possible, leading to a potentially large range of derivatives.15
i
Flgure 12 Mass spectrum of C70Ph 4
1150
mlZ
I
145
m/z
Figure 13 Mass spectra for C70Phg (above) and C7Oph10 (below)
146
Figure 14 Schlegel diagram for C7$'h,o showing n.0.e.couplingsbetween adjacent phenyl groups
pentagon. This bond is very reactive and readily undergoes addition.l6 A further notable
feature of C70Ph8 is that it is readily oxidised to a tetra-oxide which undergoes thermal
elimination of two molecules of carbon dioxide during EI mass spectrometry to give
C&hg. l6 The product of this unique degradation has not yet been fully characterised,
but possibly contains a seven-membered ring, arising from elimination of the two carbons
at either end of the reactive double bond.
Other phenyl derivatives are also present e.g., C70Ph14 but at the time of writing
have not been isolated and characterised. It is possible to selectively insert other aryl
groups into the positions occupied by the phenyl rings E in C70Ph10.~
3. Arenylation
The reaction of fbllereneswith benzyne falls properly within the category of 2 + 2
cycloadditions, described in Chapter 12, but is included here also for completeness.The
products of such reactions e.g. 1,2-benzo[60]fUllerene (1) are rather stable due to the
presence of the benzenoid ring. Consequently there is much less tendency for the retro-
ene reaction to take place during mass spectroscopicanalysis. As in the case of arylation,
the ultimate goal must be to introduce substituents into the benzenoid rings so that
fbrther derivatisation may be achieved. In the case of the benzyne adducts, electrophilic
substitutionat the P-position of the benzenoid ring is to be expected due to strain and so
the behaviour should parallel that of ag. benu>cyclobutene. 17 In order to minjmise strain
147
in the 4-membered ring, the x-bonds should be localised at the positions shown in (I),
and this will affect the directing effects of the substituents in the benzenoid ring.
Because of the need to avoid having double bonds in the pentagonal rings of
fuUerenes,l* transmission of the electronic effects of addends fiom one part of the cages
to another is poor. This accounts for the multiple additions so common (and benzyne.
[60]Fullmne adds up to six b e n y n e ~ , 1 9 ~the
~ *locations being unknown, but it may
reasonably be assumed that they are at the octahedral sites. Addition of one benzyne unit
has been shown by N M R analysis19 to take place across the 12-bond (1).
m/Z
Figure 15 Uass spectnun of the product of reaction of ['lO]fullerene with benzyne, showing that ten
groups have been added
Under extended reaction times, [7O]tbllerene adds up to ten benzynes (Fig. 151,
but the locations of the addends are not yet known.21 Addition across each of the ten
equivalent 1,Z-bonds is not possible because of steric hindrance so some other sites must
148
be involved as weli, and it was predicted that the majority of the additions must
necessarily across the 5,6-bond (see Chap. 1 for numbering) because of steric
constraints.
Two isomeric momoadducts of benzyne with [70]fullerene have been isolated. In
contrast to all other work on [70]fbllerene (where the 1,Zaddition predominates
substantially), addition appears to take place across the 5,6-bond and 1,2-bonds (see
Figure 8, Chap. 1 for numbering) in almost equal amounts.2* The difference in the
present work can be attributed to the fact that is that it is easier for the rigid benzyne
addend to bridge a less curved region of the surface (the 5,6-bond) than it is to bridge a
more curved region (the 1,2-bond). This result demonstrates a hitherto unrecognised
aspect of fullerene chemistry, and further examples may emerge in due course.
1,I-Naphthyne, produced from the pyrolysis of 1,s-di-iodonaphthalene also adds
to [(iO]fuUerene, to give the structure (2) identified by NMR and mass spectrometry
Even more intriguing is the fact that ten such naphthyne units have been shown, by mass
spectrometry to add to [60]fullerene, and it is difficult at present to see how this can be
accomplished in view of the steric hindrance that is anticipated; one possibility could be
that naphthynes add to the addends already on the ~ a g e . 2In~this work it was also found
that two [60]fbllerene molecules add to a single naphthyne molecule and a structure with
fusion across the 1,2- and 7,s-bonds was but this is sterically very
crowded. Two alternatives deserve consideration, In one, addition takes place across the
1,2- and 5,6-bonds of naphthalene, and the other is structure (3) which seems especially
favourable because strain in the 4-membered ring is reduced through use of the longer
bonds of naphthalene, and also the naphthalene canonical is the one of lowest energy.
References
1. R.Taylor, Electrophiiic Aromatic Substitution, (Wiley, Chichester, 1989), pp. 202-
203,
2. G.A.Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Sensharma, and
G. K.S . Prakash,J. Am. Chem. Soc.,113 (1991)9387.
3. S.H. Hoke, J. Molstad, G. L. Payne, B. Kahr, D. Ben-Amotz, and R.G. Cooks,
RapidCornrn. Mass Spectr. 5 (1991)472.
4. R.Taylor, unpublished work.
5 . G. A. Olah,I. Bucsi, R. Aniszfeld, and G. K. S.Prakash, Carbon, 30 (1992) 1203.
6. A. D. Darwish, unpublished work.
7. L. S.K.Pang and M. A. Wilson, J. Phys. Chem., 97 (1993)6761.
8. A. G.Avmt, A. D. Darwish, D. K. Heimbach, H. W. Kroto, M. F. Meidine, J. P.
Parsons,C.Remars, R. Roers, 0. Ohashi, R. Taylor, and D. R. M. Walton, J Chem.
Soc..Perkin Trans. 2, (1 994) 15,
9. R. Taylor, G.J. Langley, M. F. Meidine, J. P. Parsons, A. K. Abdul-Sada, T. J.
Dennis,J. P. Hare, H. W. Kroto, and D. R. M. Walton, J. Chem. SOC., Chem.
Commun.,(1 992)667.
10.A. 0.Avent, P. R. Birkett, J. D. Crane, A. D. Darwish, G. J. Langley, H. W. Kroto,
R. Taylor, and D. R. M. Walton, J. Chem. Soc.,Chern. Commun., (1994)1463.
11. P. R. Birkett, A. G. Avent, A. D. Darwish, A. K. Abdul-Sada, H. W. Kroto, R.
Taylor, and D. R. M. Walton, unpublished work.
12.R. Taylor, J. Chem. SOC.,Perkin Trans. 2, (1992)1667.
13.G.A. Olah,1. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Sensharma, and
G. K.S.Prakash,J. Am. Chem. Soc.,113 (1991)9385.
14.Ref 1,pp. 432-433.
15.Ref. 1,Chapter 10.
16.P.R. Birkett, A. D. Darwish, H. W.Kroto, R. Taylor, and D. R. M. Walton,
unpublished work.
17.R d . 1, pp. 77, 145, 150.
18.R. Taylor, Tetrahedron Lett. (1 991) 373 1 ;J. Chem. Soc., Perkin Trans. 2 (1 992)3.
19.S. H. Hoke, J. Molstad, D. Dilettato, M. J. Jay, D. Carlson, B. Kahr and R. G.
Cooks, J Org. Chem. 57 (1992)5069.
20.M. Tsuda, T. Ishida, T. Nogami, S. Kurono and M. Ohashi, Chem. Lett. (1992)
2333.
21. A. D. Danvish, A. K. Abdul-Sada, G. J. Langley, H. W. Kroto, R. Taylor, and D. R.
M. Walton, J. Chem. Soc., Chem. Commun. (1 994) 2 133.
22. A. D. Darwish, A. G.Avent, H. W. Kroto, R. TayIor, and D. R. M. Wdton,
unpublished work.
23. S. H. Hoke,J. Molstad, S. Yang, D. Carlson, and B. Kahr, J. Org. Chem., 59 (1994)
3230.
Chapter 9
'zhir chapter describes the synthesis, characterization and properties of products derived
from additiodinsertion of methylene groups (and their 0,N. and Si homologues)
acrosahto adjacentcarbons of Qo (Scheme 1).
Scheme 1
1 2
It is interesting to note that, so far, representativesof thii class are the only reported
examples of insertion reaction into a fullerene bond (structures 2, Scheme 1). This means
that this class of compounds is unique in that it gives isomers with potentially different
151
152
The formal addition or insertion of a carbene unit to a bond of c60 results in the
formation of methanofullerenes 1 (Scheme 1, X = CR2) or fulleroids 2 (Scheme 1, X =
CR2) respectively.'V2 Methanofullerenes are cyclopropane analogues, whereas fulleroids
s . ~principle, there can be two
possess structures similar to Vogel's I , ~ ~ - a n n u l e n eIn
structurally different methanofullerenes, with the cyclopropane bond fusing a 6.6 or a 5,6
junction of C a (structures 3 and 4 in Scheme 2, respectively).
Scheme 2
@ -
@ \ / '/
\
\ / '/ \
3 4
Analogously, there will be potentially two different fulleroids, with the bridge carbon
spanning over two six-membered rings or over a five- and a six-membered rings of Cm
(structures 5 and 6 in Scheme 3, respectively).
The structural assignment to the reaction products, i. e., the distinction between 3,4,
5, and 6 is a very intriguing problem, and support from any spectroscopic means is of
vital importance. In particular, I3C NMR spectroscopy plays here a fundamental role. The
detection of the l3C resonance for the bridgehead carbons in a non-aromatic region can be
diagnostic for addition products (3 and 4 vs 5 and 6). On the other hand, the distinction
between 6,6 and 5,6 junctions (3 and 5 vs 4 and 6) relies on the correct counting of 13C
resonance number. With identical R groups, adducts to 6.6 and 5.6 junctions have
153
Scheme 3
5 6
1.I. Diatomethane
Diazomethane is the simplest diazo compound. It reacts readily with c 6 0 to give the
thermally unstable pyrazoline 7 in 44% yield (Scheme 4)?
Scheme 4
A
-
@
CH2N2 + c60
- N2 / /
\ /
7 8
154
This compound is the result of addition of the 1,3-dipole to a 6.6 ring junction of C a .
When a toluene solution of 7 is heated to reflux, the parent fulleroid C61H2(8) is
recovered almost quantitatively (Scheme 4). The same product is also formed by thermal
decomposition in the solid. The 1H NMR spectrum of the dihydrofulleroid 8 shows two
doublets (with coupling constant J = 9.7 Hz) at 2.87 and 6.35 ppm in a ratio 1:l; one
hydrogen is significantly deshielded reIative to the other (A6 = 3.48 ppm). The coupling
constants between the '3C-labeled bridge carbon and the two methylene protons are:
J(13C-Ha) = 145.0 and J('3C-Hb) = 147.8 Hz.The asymmetry of the methylene group,
the 13C-H coupling constants, the absence of sp3 carbons in the 13C NMR as well as the
number of carbon signals, corroborate the 1.6-fulleroid structure with insertion into a 5,6
ring junction and a Cs symmetry?
When 7 is irradiated rather than thermolyzed, a mixture of 8 and another product is
obtained, to which the methanofullerene structure 9 has been attributed (in this case the
two protons give a singlet at 3.93 ppm, their J('3C-H) = 166.5 Hz,characteristic of
cyclopropanes, the number of signals in 13C NMR supports a CzV symmetry, with
bridgehead carbons at 7 1.0 ppm).*
Scheme 5
-
- N2
7 9
The two compounds 8 and 9 are stable and do not give any interconversion, either by
irradiation or thermolysis.8 Accordingly, it was calculated that the interconversion barrier
should be relatively high?."
chromatographically pure mixture (1H NMR, 13C NMR, HETCOR)have allowed the
attribution of structures 10-12 to the three isomers (Scheme 6).l
In particular, HETCOR analysis shows that the methyl protons at 2.52 ppm (in 10) are
connected to the bridge and bridgehead carbons resonating at 46.96 and 80.98 ppm
respectively. In the other two isomers, the methyl protons at 1.32 and 3.19 ppm couple
with the bridge carbons at 56.06 and 52.72 ppm respectively and the bridgehead carbons at
141.50 and 141.67 in the order. The relative stereochemistry of 11and 12 (methyl on 6-
or 5-membered ring) has been assigned on the basis of ring current effects (see below).
Thermal conversion of 11and 12 to pure 10 can be achieved by heating a toluene solution
of the three isomers to reflux.' This is in agreement with teoretical calulations which have
shown that methanofullerenes are thermodynamically more stable than f~lleroids.'.~*"A
reason for this difference in stability has been attributed to the violation of Bredt's rule, as
bridgehead carbons in fulleroids possess a formal sp2 ~haracter.~
Scheme 6
@ @ ' @-
/ / / /
' '\
\ /
/ \ / \ /
10 11 12
Ar = rtmethoxyphenyl
Scheme 7
C0OCH-j
CH30-f&
H J y
@ @
\
\ / '
13
/ \
\ / '
14
/
1.3. Applications
The addition of diazo compounds to Cm has proven very efficient and versatile. For
instance,diary1 methanofullerenes 15 have been pEpared with many different substituents
on the phenyl rings (Scheme 81.5
Methanofullerene 15h was further elaborated in order to prepare a water-soluble
fullerene derivative. On the basis of model building studies, it was indeed found that the
fullerene sphere fits the mostly hydrophobic active site of the HIV- 1 protease (HIVP).I7 It
was also suggested that a fullerene derivative might inhibit another HIV enzyme, i. e.,
reverse transcriptase. Design considerations required that the specifically desi ned
!
fullemne derivatives have polar functional groups at one end of the carbon cluster.' For
any experimental confirmation of this pEmise, a water soluble Cm derivative was needed.
1 57
Scheme 8
15
a, R = H; b, R = CH,; c, R = OCH,; d, R = Br; e, R = N(CH3),;
f, R = COOPh; g, R = OH; h. R = (CH,)zNHC(O)CH,
Thus, the amide groups in 1% were hydrolyzed and the resulting amino groups were
acylated with succinic anhydride.'* Bis-acid 16 (Scheme 9) was found to inhibit acutely
and chronically HIV-1 infected human peripheral blood mononuclear cells (PBMC) with
an Ecso of 7 pM,while showing no cytotoxicity in uninfected PBMCt9 as well as whole
animals (rnice)?O
Scheme 9
HOOCCH2CH2CONHCH2CH2 CH2CH2NHCOCH2CH2COOH
16
The computational work, but especially the experimental results, generated great
excitement on the possible biological applications of fullerene derivatives.
Methanofullerenes containing amino acids 1712and 1813were soon prepared, and also a
158
Scheme 10
17 18
CO(L-Ala-Aib)2-L-Ala-OMe
H
Ala = alanine
19 Aib = a-aminoisobutyric acid
fullercne unit with a greater control over the formation of polymer-fullerene hybrid
structures.
Scheme 11
f O(CH&X$-n (-NHC
20 21
N2
vN2 /
22
__cc60
Scheme 12
23
c60
N2
24 25
160
Scheme 13
26
c60
@ \
\ / '
27
/
This latter product was successfully used to exploit the possibility of analyzing fullerene
derivatives by elecaospray ionization mass spectrometry. It is also expected that 2725(and
its benzo-15-crown-5 a n a l o g ~ e )may
' ~ form host-guest complexes with selective binding
of metal ions.
It is clear from Sections 1.1 and 1.2 that fulleroids and methanofuIlerenes are formed
by nitrogen extrusion from the pyrazoline intermediate, in turn originated from
cycloaddition of the diazo compound to the most reactive double bond of Cm, i. e., the
6,6-ring junction. From a literature s e a r ~ h , ' ~it~ is
* ~easy to realize that all reactions
involving c60 occur at this site, and that 5,6-adducts (fulleroids) are formed only as
rearrangement products (see also Section 3, below). Based on this premise, it is also
reasonable to assume that, any reactive carbene will attack the same double bond of C a to
give addition products (1 + 2 cycloaddition) exclusively at the 6,6-ring junction, i. e.,
methanofullerenes.
161
Scheme 14
R = CH2Ph 28
R = COC(CH&
Scheme 15
C b C l
29
Scheme 16
30
4 0 R
x
yo
32 31
Scheme 17
33 34 35
B 4 - COOEt
- NaBr, - H2
@
\ / '
\ /
36 37
The reaction, which occurs at the 6.6-ring junction of Ca, proved valid for a variety of
nuclaophiles, generated by deprotonation of diethyl bromomalonate (36),methyl 2-
chloroacetylacetate, obromoacetophenone, and desyl chloride (and DBU as the base).30
The addition of dimethyl bromomalonate to C6o was used by Hirsch to study the
regiochemistry of multiple additions to C a (see Section 1.Q3'
The same reaction, applied to C70,has represented one of the very few examples of
functionalizationof this other fullerene. The addition gave one predominant isomer.3o
Fullemids and C a have 60 '#' electrons. and consequently, their electronic spectra are
almost superimposable (Fig. 1). The saturation of a double bond in methanofullerenes
164
0.20 1 I I I
I 0.20 ; I I 1 I
I
'1
h
Y
0.161
D
b
'ii
4
!
Fig. 1 (left). Vis absorption spectrum of 13 (solid line) and Cs0(dotted line).
Fig. 2 (right). Vis absorption spectrum of 14 (solid line) and C, (dotted line.).
The maximum in the broad band between 450 and 650 nm in C a is hypsochromically
shifted and the fiie structure near 600 nm is lost in methanofullerenes. Other characteristic
features are a sharp band near 430 nm and a weak band around 700 nm. These latter two
relatively weak absorption bands appear to be typical of all dihydrofullerenes, i. e., C6o
derivatives with a saturated double bond. ***
1.6.Electrochemical Properties
Diary1 fulleroids and methanofullerenes (15) retain most of the C6o exceptional
electrochemical properties. Little difference is observed between the two classes of
derivatives when subjected to cyclic voltammetry experiments. Both species experience a
shift of the first reduction potential to more negative values of about 100-150 mV with
respect to C a , irrespective of the substitutent on the aryl rings. It was also observed that
fulleroids may rearrange to the corresponding methanofullerenes upon taking the third
electron in solution (see above. Section 1.2).16
A particular case is represented by the spiro-annulated methanofullerenes 38 (Scheme
19). It was found that, contrary to the diary1 methanofullerenes 15, the cyclic voltammetric
behavior of 38 is very sensitive to the presence of substituents on the fluorene
~ n o i e t y ? ~With
, ~ ~electron-donating groups (38b) the reduction potentials are shifted to
more negative values, even relative to 15.
165
Scheme 19
38 39
a,R=H
b, R = N(CH,Ph),
C. R = NO2
On the other hand, the first reduction potential becomes less negative if strong electron-
attracting groups are placed in the 9-fluorenyl moiety (38~).The most remarkable case is
represented by 9-azafluorenyl-methanofullerene39, whose first potential wave is slightly
less negative than C a itself (Table 1). The effect becomes more dramatic going to higher
reduction potentials. The third and fourth steps for 38c and 39 are = 0.5 V less negative
and thus these adducts are much better acceptors than Q.
Conditions: Pt working and counter electrodes; scan rate, 100 mVk; AglAgCY3M NaC1,
reference electrode; Ferrocene internal reference (+ 620 mV); 0.1 M TEiABF4 in THF.
166
40
Not only has 40 a proton a which lies exactly on a 5-MR of the spheroid, but also has
a reference proton, i. e., a chemically equivalent proton b far from the magnetic influence
of the fullerene surface which may serve as a comparison with proton a. The 1H NMR
167
The addition of more than one carbene unit to Ca can result in the formation of bis-,
tris-, tetrakis-, pentakis- and hexakis-adducts. In the case of addition of diphenyl
diazomethane.each adduct has been isolated and characterized. Due to the high number of
possible regioisomers each chromatographically pure fraction consists of many
components which give rather broad signals in IH NMR spectra. The hexakis adduct
shows a somewhat sharper NMR pattern, where all the phenyl groups have become
equivalent. The most symmetrical arrangment. the octahedral adduct 41. may be
responsible for the simplified spectrum.6
Ph,Ph
PhAPh
41
The regiochemistry of addition has been studied in detail in the case of bromomalonate
addition in basic ambient (see Section 1.4).31 Seven bis-adducts have been separated by
preparative HPLC and characterized by UV-Vis. *Hand 13CNMR, IR spectroscopies.
The assignment of the structure is based on a combination of symmetry and polarity
reasoning. Surprisingly, the most symmetrical and less polar bis-adduct, with two
addends at opposite poles of the sphere, is the minor component (and the least soluble) in
the bis-adduct mixture. The low yield of this bis-adduct has been justified as the
statistically less favored (one site of attack versus four equivalent sites for the other
attacks).
The isomerically pure bis-adducts were separately subjected to further reaction to give
mixtures of tris-adducts. The major components in the relative mixtures were separated
and characterized. Successive reactions and separations led eventually to the isolation of
the pure symmetrical hexakis-adduct.
168
2. Fullerene Oxides
The fullerene oxide, CcjoO (42), was isolated under two different oxidative conditions.
An oxygenated benzene solution of C a was irradiated with UV-Vis light and the epoxide
42 isolated in 7% yield. Addition of benzil as sensitizer improved the yield of 42 and
accelerated the oxidation mction?
Scheme 20
42 43
In a different work, dimethyl dioxirane was employed as the oxidizing agent, and 42
was isolated along with a 13-dioxolane adduct>8
Both research groups discuss the smctute determination of the product and assign the
6.6 ring-closed (epoxide) structure 42 to the fullerene oxide based on the following: (a)
the detection of a carbon resonance at 90-91 ppm, attributed to the epoxide carbons; (b) the
number of carbon resonances (17), which is in agreement only with a symmetry
compound.
Recently, the X-ray crystal structure determination of an iridium complex of 42 has
been reported. The interatomic C-C bond distance in the epoxide was determined as 1.478
A.39
CcjoO was found to be relatively stable, although it converts back to C a either during
chromatography on neutral alumina3 or in refluxing toluene?*
Rather surprisingly, and in contrast to the case of fulleroids and methanofullerenes
(Section 1.2) theoretical calculations give the 5,6 open isomer 43 slightly more stable than
42. lo The interconversion barrier between the two isomers was evaluated to about 60-75
kcaYmol, depending on the direction. As 5,6 open compounds (1,6-fulleroids) are
probably produced only through nitrogen extrusion from a pyrazoline intermediate
(Sections 1.1 and 1.2), it should be possible, at least in principle, to prepare the 5,6 open
isomer 43 (so far never isolated) by controlled ozonization. The molozonide intermediate
might loose oxygen and then, perhaps, give the more stable 5,6 isomer or, at least, a
169
mixture of the two isomers. In a recent paper on the ozonization of CmO has been
indeed detected by mass spectrometry.40
CaOo (42) shows a UV-Vi spectrum very similar to that of the methanofullerenes(see
Section 1.5). The cyclic voltammetry of 42 has been reported/* Although CmO gives
only bversible reduction waves, differential pulse voltammetry and Osteryoung square
wave voltammetry indicate that the first duction peak is shifted to less negative potentials
relative to C a . This is unusual, as in most cases monoaddition derivatives of Ctjo are
shifted by 100-150 mV to more negative values (cf. Section 1.6). The surprising
electrwhmical behavior of CmO has been interpteted in terns of electronegativity of the
oxygen atom?*
The presence of oxygen has also been found to improve the rather poor amphiphilic
properda of Qjo. Good quality Langmuir films of 42 were obtained, probably due to the
formation of hydrogen bond interactionswith the water layer."
Scheme 21
RCHzN3
44
45
a, R = OCH2CH2SiCH3
b, R = C,H,
R = 4-OCH3-C,H,
C.
d, R = 4-Br-C6H4
The major problem in attributing the correct structure to A was the detection (for Aa) of
a 1% resonance as low as 159.8 ppm for two equivalent carbons bound to the nitrogen
170
bridge. This, of course, necessarily ruled out the possibility of a triazoline, the obvious
intermediate in the 1.3-dipolar cycloaddition of azides to olefins.
The cyclic voltammetry of 45 shows that the reduction potentials are shifted to more
negative values relative to Cm, showing that the electronegative atom plays a minor role in
this case (cf. Section 2).
Azamethanofullerenes (or fullerene aziridines) have been obtained in the addition of
azido formic esters to Cm (Scheme 22).''''-&
Scheme 22
@ R = COOCH2CH3
R = N-phthalimido
R = C00-2,4,6-ui-t-butyl-phenyl
\
\ / '/
46
The contrast with the formation of azafulleroids reported above for the addition of alkyl
azides is only apparent, as in the present case addition of nitrene species directly to a 6.6
ringjunction of C a may be operative.
4. Eullerene Siliranes
Scheme 23
hv c60
DipzSi(SiCH,), c Dip2Si:
47
48
Dip =
5. Conclusions
6. References
Figure 1. Buckminsterfullerene (c60.1). The back side of the sphere is not shown.
Cyclopentadiene
The reaction of Qo with cy~lopentadiene~~~ was among the first reported chemical
reactions of a fullerene. Diels-Alder reactioris normally occur between electron deficient
dienophiles and electron rich dienes, and low dienophile LUMO energies facilitate the
reaction. In practice, the Diels-Alder reaction of C6o with cyclopentadiene is a facile
process, taking place rapidly at room temperature. Dissolving C a in neat cyclopenta-
diene results in the addition of as many as 15 equivalents of the diene.4s5 The mono-
adduct 2 has been prepared in 74% yield by careful treatment of C6o with a slight excess
(1.2 equivalents) of cyclopentadiene in benzene solution at room temperature, and
purified by flash chromatography on silica gel using a hexane-dichloromethanemobile
phase?.' The Cs symmetry, resulting from [4+2] addition across a double bond (the 1,2
positions) at the fusion of two six membered rings of C& was assigned based on the *3C
N M R spectrum. A total of 34 lines are expected in the 13C spectrum, and 33 are
observed, with one line presumably obscured by a solvent (benzene) resonance.
174
175
2
Intenstingly, 33 lines are also expected for the product of addition across the 1,2
positions (3). This [6+4] mode of addition can not be distinguished from [4+2] addition
across the 1,4 positions by 13C NMR. but is not likely since it forces two double bonds to
localized in five membered rings, an arrangement that is not favorable.*v9 Crystal
structures of other Diels-Alder adducts (see below) have confirmed a [4+2] mode of
addition a m s s the 1,2 positions.
3
The Cgj-cyclopentadieneadduct 2 is found even in crude fullerene extract prepared
from soot produced in oxygen-poor benzene flames.6 This surprising result is due to the
natural Occumnce of cyclopentadiene in flames, and the apparent cycloaddition of the
two components either in the flame or, more likely, in the soot or tolueqe extract thereof.
Cycloreversion of 2 to C a and cyclopentadiene occurs quite easily, proceeding quickly
at 95 'C.6
The cycloreversion of 2 complicates the mass spectrometric analysis of this
compound and others.6*'0 Reduction of 2 with a slight positive pressure of hydrogen over
Pt02 catalyst produces 4 (Eq.21, which is substantially less prone to cycloreversion in the
mass spocmmeter than the parent 2.7 Under these reaction conditions the Qo moiety in
2 (and @ itself) is unreactive. Tieatment of 2 with bromine (1 equivalent) produces
dibromide 5 in which only the cyclopentene moiety has undergone bromination (Eq. 3).
While &reacts with neat bromine," it does not react with dilute solutions of bromine,"
and the fullcrene moiety in 2 is clearly less reactive than the cyclopentene moiety.
176
H2 (75 rnm)
c
PtO*
Br
CH3
HF
6 7
Anthracene
Anthracene forms a Diels-Alder adduct with Ca,although higher temperatures are
required? The monoadduct (8) can be obtained in 13% yield after heating Ca with 10
equivalents of anthracene in refluxing toluene for three days, and purification with
177
column chromatography on silica using CS2 as the mobile phase (Eq. 4).16 The use of
molten naphthalene as solvent increases the yield of this reaction to 6796.
Cyclmversion occurs between 120 C and 190 C in the solid state (by -A).
8
The nversibility of the Diels-Alderreaction of Cm with cyclopentadieneand with
anthractne has lead several research groups to investigate methodology that would render
the addition irreversible. Reaction of Q,o with diene 9 over 5 hours at 110 C produces
11 in 60%yield. The initial adduct 10 is an unstable 7-oxonorbornadienewhich
undergoes rapid, spontaneous loss of CO, producing 11 which is stable toward
cyclmersion (Eq. 5).18 Crystallography revealed that 11 adopts a boat conformation in
the solid state; the activation barrier for boat-boat interconversionis 14.6 kcaymole as
measund by variable temperature NMR. This barrier is 7 kcal/mole higher than the
barrier for cyclohexene.
c
/
10 11
12 13
14 15
This methodology has been extended to the preparation of fullerene derivatives
containing ionophores?O
The other isomer of 13, p-xylylene (17). can be prepared by pyrolysis of
paracyclophane (16). Cycloadditions of p-xylylene and Ca are not possible and radical
polymerization occurs (Eq. 71.2~The resulting Cm-xylylene copolymer contains on
between three and four p-xylylene units per C a unit and is thermally stable to 475 'C.
\ /
16 17
19
179
20 21
22 23
Acycllc l,3=Dienes
A similar approach has been used to construct fullerene-containingdonor-acceptor
systems with a rigid bridge se mating the electron donor group @-dimethoxyphenyl)
from the acceptor (fullerene).% Slow addition of the 1.3-diene 24 to a hot solution of
produces 25 in virtually quantitativeyield based on unrecovered C a (63%yield, 99%
based on UNtcOvered Ca).% Crystallography revealed that, as in quinodimethane
adducts, the cyclohexene fused to the fullerene in 25 adopts a chair conformation in the
solid mtc.
24
25
An httresting study, comparing the reactivity of Ca with other dienophiles, has
suggested that Ca i s about as reactive as N-phenylmaleirnide in Diels-Alder reactions
180
with acyclic 1-phenyl-1.3 dienes (26).= Yields of 27 in these reactions range from 25%
(R = CH3) to 34% (R = H).
R
R
&02> cm
PhH, room temp. r 0 - l (12)
O C O J
26 27
Oxygenated Dienes
Oxygenated 13-dienes add to Qjo under fairly mild conditions. Heating a mixture of
and diene 28, followed by silica gel chromatography, produces ketone 29 in 59%
yield from Qjo. Further functionalintion of 29 has been achieved through reduction of
29 with diisobutyl aluminum hydride (DIBAL) in toluene, which produces alcohol 30 in
93% yield (Eq. 13). This alcohol has been acylated with protected amino acids using
standard DCC methodology to produce peptides as esters with 30?6
0
c,
YMS
c
/ toluene. reflux
53%
28 29
30
The fullerene group exerts a strong influence on the *HNMR chemical shifts of
protons on the cyclohexanone ring of 29. A difference of over 2.5 ppm is observed for
one of the protons (Ha)relative to protons at the 2-position of cycbhexanone. Variable
temperature N M R experiments have shown that the activation bamer for interconversion
of cyclohexanonering conformations in 29 is 12 kcalhnole, which is substantially higher
than the barrier in cyclohexanone itself, so it is clear that the fullerene group can
influence the normal behavior and spectroscopy of substituents.
Even more highly oxygenated dienes participate in Diels-Alder reactions with %.
Diene 31 (Danishefskys diene) adds readily to & to produce, after acid hydrolysis of
the resulting silyl enol ether, ketone 32 in 39% yield.= Treatment with trifluoroacetic
acid results in elimination of methanol, giving enone 33 (Eq.14). Mass spectrometric
181
analysis of 33 only showed the m/e 720 line correspondingto Ca rather than the parent
ion canespondin to 33, sug esting that cycloreversionis facile under FAB conditions.
Tagging 33 withi6 (R = H) !ollowcd by electrospray MS resulted in a derivative that
could be analyzed by elecaospray mass spectrometry,a technique mild enough for the
enone to survive.
2. H30+
-
TFA
0
(14)
oc&
31 32 33
..
-diton reactions almost invariably involve heteroatoms at one or
both terminus of the 1.3 dipole, and as a result these reactions form new carbon-
heteroatom bonds as well as new carbon-carbon bonds. The reaction of Ca with a
variety of different 13dipoles have been reported, and one of these, the addition of
diazoaliranss, is the most highly developed reaction in fullerene chemistry. This reaction,
and the addition of alkyl azides as well, are fully discussed elsewhere and therefore will
be discussedin a most cursory fashion here.
Diazaelkanes
Heating a solution of (trimethylsily1ethoxy)methyl azide (34) and Cm in
chlorobenzeneproduces two products, one of which is identified as azafulleroid 35 (30%
yield), &e other of which (24% yield) is converted to 35 upon heating. The 1,3-dipolar
addition of azides to Ca presumably proceeds through mazole intermediate 36,but 36
itself is not observed. Instead, the reaction produces the equivalent of nitrene insertion,
resulting in fullemid type structure 35 (Eq.15).27 A number of other alkyl and aryl
azides undergo similar reactions?*28
ms-ofiN3
c,
Phcl mflux - (15)
34 35
L
36
182
37
Methanofullerenes have also been prepared by the addition of diethyl bromomalonate
anion to ~ 6 0 . 3 6 3 7
Nitrile oxides
Nitrile oxides 38 also react as 1,3 dipoles with C a , producing A24soxazolines39 as
products3839 in yields that are typically 35% (65% based on recovered Q) after
purification by gel permeation chromatography (Eq. 16).38 The cycloaddition has proven
to be quite general and has been used to produce a number of compounds with different
substituents at C-3.
38 39
R = Me, Et, COzEt, Ph, PhOMe, (CH2)&02Et
The 13C N M R spectra of these compounds indicate that the addition takes place
across the 1,2 positions (a 6-6 ring fusion). The correct number of lines are observed in
the I3C spectrum, consistent with the Cs symmetry of 39. These similarities support the
structural assignment over a fulleroid-type struchire.
These compounds are highly resistant to cycloreversion and are stable in solution
above 250 'C for extended periods of time. They are also resistant to most of the reagents
that are commonly used to reductive13 cleave isoxazoline rings. Nitrile oxides also add to
C70 to produce a mixture of isomeric monoadducts in a roughly 1:1:1
Sulfinimide 40 undergoes 1,3-polar addition with excess Cm to produce isothiazole
4 1 in 14% yield after purification by GPC, along with small amounts of diadduct (Eq.
183
17):' The use of a large excess of 40 leads to the formation of a hexaaduct, obtained in
high yield (97%) but as a mixture of isomers.
40 41
The 1% NMR spectrum of 41 provided good evidence for addition across the 1.2
positioaa (a 6,6 ring fusion). The appearanceof a single unsplit resonance, different from
that of the starting mateiai, is expected from this mode of addition and addition across
other positions would product two different 19F signals.
Methyhecyclopropene
Hating methyknecyclopropene42 provides access to a mmethylene methane
(TMM) derivative which undergoes cycloadditionto C a to form two products, ketene
acetal43 in 34% yield and ester 44 in 27% yield after purification (Eq. 18).
K
O<
42
43 44
The mode of addition (across the 1,2 positions) was proven by the 1H Nh4R spectrum,
which shows a singlet for the CH2 group in the cyclopentane of 44. Ester 44 is not
formed directly, but is believed to result from hydrolysis of ketene acetal45 in the course
of silica gel chromatography (Eq.19).
184
4s 44
This ester has proven to be highly versatile, and can be converted to a number of
derivatives, demonstratingthas chemical manipulationscan be performed on the sjde of a
fullerene derivative without adverse reactions on the fullerene nucleus itselfP2 These
reactions include acylation of the primary hydroxyl using acid chlorides or by using DCC
and Boc-protectedamino acids, and acetalizationof the primary hydroxyl. Even more
remarkably, oxidation of the primary hydroxyl can be accomplished using PCC,the
resulting aldehyde can be reduced back using EtsSiH and Tick, and Wittig chemistry is
also successful, again without undesired reactions on the fullerene moiety.
Other trimethylenemethane species form stable cycloadducts with C a . Thermolysis
of 46 in the presence of C a leads to 47, although this could not be separated from
unreacted Ca by chromatography.
46 47
Palladium-mediated addition of TMM to Cjo has been successfully canied out. In
this case, the cycloaddition involves treatment of a preformed G - P d complex with
M~=C(CH~TMS)CH~OAC, a common Th4M pre~usor?~
Carbene Adducts
Cyclopropene48 is a precursor for a functionalized allylic carbene (49) that
undergoes addition to c60 to produce two different products resulting from different
modes of addition.44 Thermolysis of 48 in o-dichIorobenzenesolution in the presence of
'& leads to the formationof ketene acetal50, which was immediately hydrolyzed to the
correspondingester 51, isolated in 44% yield after silica gel chromatography (Eq. 21).
48 49 50
185
51
The structure of 51 (R = H) was determined by 13C N M R spectroscopy. A total of 39
lines were observed, indicating a highly symmetrical adduct. A double intensity
resonance at 75.2 ppm was assigned to the fullerene sp3 carbons. In addition, the large
~Jc-H coupling constant for cyclopropane C-H is consistent with this structure. These
adducts show no tendency to rearrange to fulleroids, even at elevated temperatures (200
T).
Cyclopmpanes (50) result when R is hydrogen or phenyl. but the reaction takes a
different course when R is ethyl, resulting in the formation of cyclopentenone ketal52.
\
CH2CH,
48 (R = Et) 52
Ammethine ylides
Several different ammethine ylide 1.3-dipoles have been added to Cm. Pyrolysis of
aziridine 53 produces ylide 54, which adds to to form 55 in 40% yield (73% based on
the conversion of %)P5
53 54 55
Heating a mixture of sarcosine (56) and paraformaldehyde in toluene has been used as
a route to ammethine ylide 57, which undergoes 1,3-dipolar addition to C+joto form
pyrrolidine 58 (41% yield, 82% based on C a c o n ~ e r s i o n ) .A~ series
~ of electroactive
femne-substituted fullerenes have been prepared in this manner?6
186
56 57 58
Oxamlidinone 59 decomposes to an azomethine ylide in refluxing toluene and has
been used to produce pyrrolidine 60 in 72% yield based on recovered Q (Eq. 25).'5
This compound has been converted to new derivatives, including the dansylated d n e
61?5
59 60
N-Dns
61
Acid treatment of 62 also produces an azomethine ylide (63). which reacts with &
to give 64 in 50% yield (90% based on recovered starting C ~ O ) ? ~
64
Disilolanes
Photolysis of a solution of disilirane 65 and % with a high-pressure mercury arc
(kc300 nm) leads to the formation of disilolane in high yield (82%).48 This reaction is
187
(Mcs)#i
,<HZ
-Si(h4-h
-b.c,
(27)
65 66
67
When limited amounts of benzyne are used, significant amounts of monoadduct can
be formed. At 72% conversion, the monoadduct 67 was obtained in 45% yield, the
double adduct was present in 38% yield, and the triadduct and tetraaduct in 12% and 2%
yield respectively (all as judged by mass spe~trometry):~The reaction mixture was
separated by C18 reversed-phaseHPLC into the different adducts, but individual isomers
of the Wer adducts were not separated.
Quadxicyclane (68) also undergoes thermal [2+2] addition to C ~ OAdduct . ~ 69,
obtained in 43% 'eld after purification by GPC, is subject to electrophilicattack by
phenyl nulfim~lcgoride, roducing chloride 70 in quantitative yield (Eq. 29). Addition
across a 5,6 nng fusione!t( 2.3 positions) would result in an adduct of the same
symmetry and the same number of resonances in the l3C NMR spectrum, it is believed
that this reaction proceeds at a 6,6 ring fusion (the 1,2 positions) for orbital symmetry
reasons and to avoid localizing a double bond in a five member ring.*
188
ci
68 69 70
K HSO,. HzO
dioxane. PhCH,
100%
71 72
73
..
u+21Photocvcloaddltlons
Photopolymerization
During a study of the laser Raman spectra of thin films of C a , the Raman-active
pentagonal pinch mode of solid Q was observed to shifts2from 1469 cm-1 to 1458 cm-1
after laser irradiation in the visible or UV at laser fluences greater than 50 m W / m 2 . The
region where the laser had illuminated the film became insoluble in toluene, and laser-
desorption mass spectromemc analysis of theses films revealed that oligomers (&$),
where n = 1 to 20, were present. Based on these data, a laser-induced [2+2]
photopolymerization of the fullerene film was proposed, leading to extended three-
dimensional network as shown in figure 2.
189
Ynamhes
Ynamines, N,N-dimethylaminopropyne(74) in particular, undergo [2+2]
photoaddition to %to d u c e cyclobutenes 75 in excellent yield (Eq. 31).55 Unlike
most cycloadditions of &. the reaction can be driven nearly to completion without
signiflcant interference from the formation of poly-adducts. A long wavelength light is
used, and is absorbed more strongly by the Gjc~starting material than by 72.
74 7s
78 77
Of particular interest is the hydration of 75. The mechanism proposed for this
reaction implies that in the ring-opening step, a fullerene anion is a better leaving group
than an amine. Given the very low pK for a fullerene-hydrogen bond (5.7 for tBu-
Ws8 ), this seems plausible.
Enones
Fullerene derivatives are reactive in 12+21photocycloadditions. Irradiation of
itself with cyclohexenone in toluene solution to 25% conversion provided adduct 78 (R =
H)in 20% yield after chromatography on silica gel (Eq. 33).59 Similar results were
obtained with 3-methyl-2-cyciohexenone (R = CH3). Under appropriate conditions, as
many as seven enone units were added to the fullerene, and this photocycloaddition is
successful on methanofullerenes as well as on Ca itself.
78
191
Coneluafons
The Cm fullerene is a reactive 2~ electron component that participates in a wide
variety of cycloaddition reactions but does not function as a 4rr component, despite the
presence of diene substructures. Addition occurs invariably involves the 1,Zdouble bond
(the 6,6-ring fusion). Fullerenes react with many different 1,3-dienesin good yields to
give Diels-Alder products that are often stable toward cycloreversion. The cyclohexenes
f o m 4 adopt boat conformations,although some are conformationallymobile on the
N M R dme scale.
The addition of a variety of carbenes, 1,3-dipoles,and trimethylenemethaneshave
been x r tcd ,and these adducts tend to be very stable toward cycloreversion. While
diazo ne adducts (pyrazolines) will decompose by loss of nitrogen. adducts of C2jo
with azomethineylides, nitrile oxides, and sulfinimines tend to be thermally stable to
high mmture.
Chemical manipulationsof the cycloadducts have been success in a number of cases.
The production of single isomers of chemically versatile fullerene derivatives makes
cycloadditionsthe most productive route to the preparation of novel fullerene derivatives.
192
References
Comprehensive Organic Synthesis;Paquette, L. A., Ed.; Pergamon Press: New
York, 1992; Val. 5.
Camthers, W. Cycloaddition Reactions in Organic Synthesis; Pergamon Press:
New York, 1990; Vol. 8.
Henderson. C. C.; Cahill. P. A. Science 1993,259, 1885-1887.
Wudl, F.; Hirsch. A.; Khemani. K. C.; Suzuki, T.; Allemand, P.-M.; Koch, A.;
Eckert, 3.; Srdanov, G.; Webb, H. M. In Fullerenes: Synthesis, Properties, and
Chemistry of Large Carbon Clusters; G . S . Hammond and V. J. Kuck. Ed.;ACS:
Washington, DC, 1992; Vol. 481; pp 161-175.
Tsuda, M.; Ishida, T.; Nogami. T.; Kurono, S.; Ohashi, M. Chemistry Lett. 1992,
2333-2334.
Rotello, V. M.; Howard, J. B.; Yadav, T.; Conn, M. M.; Viani, E.; Giovane, L.
M.; Lafleur, A. L. TerrahedronLett. 1993. 1561-1562.
Meidine, M. F.; Roers, R.; Langely, G. J.; Advent, A. G.;Darwish, A. D.; Firth,
S.; Kroto, H. W.; Taylor, R.; Walton. D. R. M. J. Chem. SOC.,Chem. Commun.
1993,1342-1344.
Matsuzawa, N.; Dixon, D. A.; Fukunaga, T. J. Phys. Chem. 1992.96.7594-7604.
Dixon, D. A.; Matsuzawa, N.; Fukunaga, T.; Tebbe, F. N. J. Phys. Chem. 1992,
96,6107-6110.
Howard, J. B.; McKinnon, J. T.; Makarovsky, Y.; Lafleur, A. L.; Johnson, M. E.
Nature 1991,352, 139-141.
Tebbe, F. N.; Harlow, R. L.; Chase, D. B.; Thorn, D. L.; Campbell, G. C.;
Calabrese, J. C.; Herron, N.; Young, R. J.; Wasserman, E. Science 1992,256,
822-825.
Meidine, M. F.; Avent, A. G.;Darwish, A. D.; Kroto, H. W.; Ohashi, 0.; Taylor,
R.; Walton, D. R. M. J. Chem. SOC. Perkin Trans. 2 1994, In Press.
Balch, A. L.; Catalano, V. J.; Lee, J. W.; Olmstead, M. M.; Parkin, S. R. J . Am.
Chem. SOC. 1991,113,8953-8955.
Balch, A. L.; Lee, J. W.; Olmstead, M. M. Angew. Chem. Int. Ed. Engl. 1992,31,
1356-1358.
Hawkins, J. M.; Meyer, A.; Solow, M. A. J. Am. Chem. SOC. 1993,115,7499-
7500.
Schlueter, J. A.; Seaman, J. M.; Taha, S.; Cohen, H.; Lykke, K. R.;'Wang, H. H.;
Williams, J. M. J. Chem. SOC. Chem. Comm. 1993,972-974.
Komatsu, K.; Murata, Y.; Sugita, N.; Takeuchi, K.; Wan, T. S. M. Tetrahedron
k t t . 1993,34,8473-8476.
Rubin, Y.; Khan, S.; Freedberg, D. I.; Yeretzian, C. J. Am. Chem. SOC. 1993,115,
344-345.
Belik, P.; Gugel, A.; Spickermann, J.; Miillen, K. Angew. Chem. Int. Ed. Engl.
1993,32,78-80.
Giigel, A.; Kraus, A.; Spickermann, J.; Belik, P.; Miillen, K. Angew. Chem. fnt.
Ed. Engl. 1994,33,559-561.
Loy, D. A.; Assink, R. A. J. Am. Chem. SOC. 1992,114,3977-3978.
Prato, M.; Suzuki, T.; Foroudian, H.; Li, Q,; Khemani, K.; Wudl, F.; Leonetti, J.;
Little, R. D.; White, T.; Rickborn, R.; Yamago, S.;Nakamura, E. J. Am. Chem.
SOC. 1993,115, 1594-1595.
Paddon-Row, M. N. Acc. Chem. Res. 1994,27, 18-25.
Khan, S. I.; Oliver, A. M.; Paddon-Row, M. N.; Rubin, Y. J. Am. Chem. SOC.
1993,115,4919-4920.
193
1993,130,.745-747.
Yamago, S.; Tokuyama. H.; Nakamura, E. J. Org. Chem. 1993,58,4796-4798.
Shiu,L.-L.; Lin, T.-I.; Peng, S.-M.; Her, G.-R.; Ju, D. D.; Lin. S.-K.; Hwang, J.-
H.: Mou, C. Y.: Luh, T.-Y. J. Chem. SOC.Chem. Commun. 1994,647-648.
Tokuyka, H.;-Nak&ura, M.; Nakamura, E. Tetrahedron Lett. 1993,34,7429-
7432.
Maggini, M.; Scorrano, G.; Prato, M. J. Am. Chem. SOC. 1993,115.9798-9799.
Maggini, M.; Karlsson. A.; Scorrano, G.; Sandonh, G.; Farnia, G.; Prato, M. J.
Chem. SOC.,Chem. Commun. 1994,589-590.
Zhang, X.; Willems, M.; Foote, C. S . TetrahedronLett. 1993,34,8187-8188.
Akasaka, T.; Ando, W.; Kobayashi, K.; Nagase, S . J . Am, Chem. SOC. 1993,115,
10366-10367.
Hoke, S . H. I.; Molstad, J.; Dilettato, D.; Jay, M. J.; Carlson, D.; Kahr, B.; Cooks,
R. G. J. Org. Chem. 1992,57,5069-5071.
h t o , M.; Maggini, M.; Scorrano, G.; Lucchini, V. J. Org. Chem. 1993,58,3613-
3615.
Yamago, S.; Takeichi, A.; Nakamura, E. J . Am. Chem. SOC. 1994,116, 1123-
1124.
Rao, A. M.; Zhou, P.; Wang, K.-A.; Hager, G.T.; Holden, J. M.; Wang, Y.; Lee,
Eklund, P. C.; Cornett, D. S.; Duncan, M. A.; Amster, I. J.
W.-T.; Bi, X.-X.;
Science 1993,259,955-957.
194
(53) Zhou, P.; Dong, Z.-H.; Rao, A. M.; Eklund. P. C. Chem. Phys. Lett. 1993,211,
337-339.
(54) Akselrod, L.; Byren, H. J.; Thompson, C.; Both, S. Chern.Phys. Lett. 1993,215,
131-136.
(55) Zhang, X.; Romero, A.; Foote, C. S. J . Am. Chem. SOC. 1993,115,11024-11025.
(56) Arbogast, J. W.; Foote, C. S.;Kao, M. J . Am. Chem. SOC. 1992,114,2277-2279.
(57) Arbogast, J. W.; Darmanyan, A. P.; Foote, C. S.; Rubin, Y.;Diederich, F. N.;
Alvarez, M. M.; Anz, S. 1.; Whetten, R. L. J . Phys. Chem. 1991,95,11-12.
(58) Fagan, P. 3.; Krusic, P. J.; Evans, D. H.;Lerke, S. A.; Johnston, E. J . Am. C k m .
SOC. 1992,114.9697-9699.
(59) Wilson, S. R.; Kaprinidis, N.; Wu, Y.; Schuster, D. I. J . Am. Chem. Soc. 1993,
1IS,8495-8496.
(60) Wilson, S. R.; Wu, Y.;Kaprinidis, N. A.; Schuster, D. I. J . Org. Chem. 1993.58,
6548-6549.
Chapter 1 1
Formation of Anions and Electrophilic Addition
Roger Taylor
The strong electron withdrawal by the fillerene cages makes them very
unreactivetowards most electrophiles.However this obstacle can be reduced because the
cages readily add electrons to give anionic species. Hitherto, these negatively charged
derivativesof lllerenes have been referred to generally, and sometimes rather loosely, as
fbllerides. Before discussing the chemistry it is necessary to review the ways in which
anions can be formed, and describe the correspondingnomenclature:
1. Anions formed by proton loss from a hydrogenated fbllerene (there are no
examples yet) should be called e.g. 1,2-dihydro[60]fiUeren-l-ide (loss of H+ from
position 1).
2. Anions formed by addition of a negatively charged nucleophile are called e.g. ,
2chloro[60]fbllerenel-uide (addition of CI-to position 2, charge at position 1).
3. Addition of a single electron gives rise to a radical anion and radical anions
should be described either as hllerene radical anions or as e.g. fidlerene-1-elide, where
the anion is located at the 1-position.
In the literature to date there has been conhion as to the species produced by
electron addition, and these have, more often than not been referred to as anions when in
fact they are radical anions.If an even number of single electrons are added it is possible,
though by no means certain (because delocalisation of electrons over the fbllerene
surface is poor) that the spare single electrons will combine to form a bond, giving a true
anion. However, if an odd number of electrons are added, then a radical anion must be
produced.
1. Electron Addition
Up to six electrons can be reversibly added, either electrochemically or by
reduction with sodium in liquid ammonia, to each of [60]-and [irO]fullerenes to give up
to Cm6' and C?o6-,respective1y.I For [84]fillerene up to five electrons have been
electrochemically added2 to give C8405-,though it is probable that six can be
accommodated altogether (see below).
The locations of the added electrons for [60]-and [70]fbllerenes can be
reasonably assumed to be at the pyracyclene units (Fig. 1, cf ref. 3) there being six of
I nc
196
these. The advantage of such addition is that as well as creating aromaticity in the
pentagonal rings, the octahedral location of the pyracyclene units in [60]fUllerene results
in the creations of eight isolated benzenoid rings with increased delocalisation(see Chap.
3). For [70]fillerene, addition at the pyracyclene units will produce an aromatic
equatorial region somewhat related to that proposed to exist in C70H-36;~both the D2
and D2d isomers of [84]%llerene also contain six pyracyclene moieties in their
structures. [76]Fullerene has been shown, electrochemically, to add up to five
electron^^^^ (possibly a sixth) whilst [78]fillerene also adds six electrons.6 Neither
(60]-, [70]-, [76]-, [78]-, nor [84&llerenes undergo single-electron reversible oxidation
(electron removal from the cage)6, and in the case of [76]fillerene, this contrasts with an
earlier claim to the contrary
If the fillerene cage has electron-donatinggroups attached then one could expect
that electron attachment will be more difficult. This has been demonstrated to be the case
with [60]fidlerene possessing Ni, Pd, or Pt ligands, for here the number of reversible
reduction waves observed electrochemically is reduced 7
The picture is however rather more complicated than indicated by the above
analysis, as indicated by the reactions of the anions with electrophiies, for more than six
groups are ultimately added to the cages, and this is discussed firther below.
Research to date has concentrated on (a) methods of making the anions (and of
[60]fbllerene in particular), and (b) adding as few electrons as possible to the cage.
Compared to the intensive effort being devoted to the production of cycloadducts, this
area has been relatively neglected A difficulty is perceived to be the formation of the
monoanions and hence derivatives, the problem being compounded of course by the fact
that the addition sites are relatively isolated from one another, so that there is no great
197
P
bonds into pentagons which is a dest ilising feature.8 Thus for example it is possible to
produce doubly-charged anions 9f both [60]- and [70]lllerenes in the gas phase,9
something that is generally verydicult for other species.
Delocalisation of electrons is thus local rather than global. The strong electron
withdrawal by the cages is evidenced by the failure of trifluoroacetic acid to protonate
the mono (radical) anions C6oo- and C7oo- ,lo and this provided an early indication of
the highacidity of hydrogenated hllerenes (at least of low hydrogen content).
For synthetic applications it is desirable to have the monoanion in the condensed
phase, and good progress has now been made towards achieving this goal. The radical
anion of [60]lllerene can be made by reaction with co-ordination compounds to give
chargetransfer complexes. These are generally insoluble in non-polar solvents but
soluble in polar ones. Hence if reaction is carried out in the former, precipitation can be
achieved by adding the latter. For example, reaction of [bollllerene with CrnPPh3 in
THF/tohene resulted in reduction of the lllerene and oxidation of CrII to Crm, co-
ordinated to tiphenylphosphineand THF. This gave an ESR signal at g 1.995, ascribed
to C60e'.11 Stable salts derived from this radical anion have been obtained by reaction
of [Soffiruerene with cobaltocene, dibenzo-l8-crown-6/Na, and N-
methylimidezole/tetraphenylporphinatotinIv.12 The electron-reservoir complex
[F&c*~)(C+fe6)](X) has been used to transfer either one, two, or three electrons to
[60]fbllerene to give the corresponding and isolable paramagnetic salts oct>n c60n0' (n
-
= 1 3). The singly- and doubly charged species here gave ESR signals at g 2.002, but
the triply-charged species gave a value of 2.004 with a marked dependence of linewidth
upon temperature.l3 This reflects a general feature which is the increase in g value for
the ESR signal, with increasing charge on the radical anionk 14 and the reasons for this
have been discussed in detail.15 Of particular note is the CT complex formed between
tetrakis(dimcthy1amino)ethylene (TDAFi) and [60]hllerene, which undergoes transition
to a ferromagnetic state at 16.1 K, which is ca 30 times higher than that obsewrved for
any previous organic molecular ferromagnet.16 Unfortunately it shows no remanence,
and so there is no obvious application of this property at present.
Discrete salts C60n0- (rt = 2, 3) have also been obtained by reaction of
[6O]lllerene with sodium (xs.)/THF in the presence of either two, or three equivalents of
dibenzo-[ 18]-crown-6. Cation metathesis with bis(tripheny1phosphine)iminium
chloride, [PPNICI produced less soluble, but analytical purer salts
198
[pPN]3[C ~ O[CI].MeCN
] and [PPNI-3[c6o] [C1],2MeCN. (A single crystal X-ray
structure of [PPN+]2[c602'-] showed that the anion has a slightly elongated structure,
as expected because of mutual repulsion of charges localised on opposite sides of the
cage).l8 In a related approach, the radical anionic species Na+[c6o]'-(m)5 was
prepared by reducing [60]hllerene with Na[Mn(q-CgMe5)2]-. This also gave an ESR
signal (centred at g 1.999), and, as in the case of other fbllerene anionic species, the
solvent could not be removed completely without degradation occurring.l9 ESR spectra
have also been obtained for the radical anion formed by reaction of [60]hllerene with
Na/THF at low temperature (g, 2.009) and with Li, K, and S X ~ I ~ . ~ O
Electrocrystallisationhas been used to prepare from [60]hllerene, anionic salts in
a particular oxidation state, the technique being dependent upon the salt precipitating
from the solvent employed, though this feature is not always achieved. Crystallisation is
aided by the use of a bulky cation, and the following are examples of salts produced so
far: [ P ~ P + ] ~ [ C ~ O ] - [ C (which
I ~ - ] ~behaves
. ~ ~ as a semiconductor at room temperature)
( P ~ ~ P ) ~ N + . C ([~PO
~ P- ,+~] ~ [ C ~ O - ] [(WW
I - ] ~ 1),23 and [ P ~ P + ] ~ [ C ~ O - ] CThe
I-.~~
tetraphenylphosphoniumsalts are stable in air, and in the latter compound, the hllerene
lies at the centre of a P8 cube. Insolubility is increased by going to a high reduction level.
Thus whereas the potassium salts of C6on- (n = 1-4) are soluble in liquid ammonia, those
for n = 5,6 are not and precipitate out of solution.lf Electrocrystallisation using
tetraphenylarsomiumhalides has also been achieved.25
The best method to date for preparing the monoanionic salts would seem to be
the reaction of [60]hllerene with potassium in THF,mediated by I-methylnaphthalene,
which gives a 94% yield of [C,jo]'-K+.THF. This also shows a (temperature-dependent)
ESR signal, with ag-value of 1.9987.26
radical auion having a window of stability of cu. 0.45 v. Thus, by controlling the applied
potential, the desired anion radical can be obtained, and this gives a degree of control not
readily achieved by other methods.1d
The use of this mahod has been demonstrated in the selective electrosynthesisof
MezCm. Electrochemical control produced fist the di(radical)anion, and then reaction
with methyl iodide resulted in electrophilic addition of methyl giving MgC60. Two
isomers were produced, believed to contain the methyl groups in either a 1,2- or a 1,4-
arrangement (Fig. 21.27
Whilst much less control is obtained by using radical anions obtained by reaction
with alkali metals, the products nevertheless pose interestingquestions as to where the
addends are located. For example, reduction of [60]Werene with lithium, followed by
reaction with methyl iodide gave a product containing up to cu. 24 methyl groups.28The
anions here are believed to possess an even number of electron only, since sharp I3C
NMR signals, indicating diamagnetic species, were obtained. Interestingly, species
possessing either 6 or 8 methyl groups were dominent in the spectrum, and these three
addition levels are exactly the same as obtained in bromination (Chap. 7) indicating that
common location sites for the addends are likely.
Even more methyl groups, i.e. 32, added to the cage by reduction of
[6O]lllsrsne with potassium followed by reaction with methyl iodide.29 Interestingly,
s u b l i i o n produced a product C6o(Me),, n = 2-12, with the compound n = 6
especially prominent. This work suggests that isolation of individual components in this
way d d be possible. There would seem to be scope here for examining the addition of
a range of bulkier electrophiles to determine the correlation between their size and the
maximum number that become attached to the cage.
200
References
1. (a) P.-M. Allemand, A. Koch, F. Wudl, Y. Rubin, F. Diederich, M. M. Alvarez, S. J.
Anz, and R. L. Whetten, J. Am. Chem. Sac., 113 (1991) 1050; @) D. M. COX,S .
Behal, M. Disko, S. M. Gorun, M. Greaney, C. S . Hsu, E. B. Colin, J. Millar, J.
Robbins, W. Robbins, R. D. Sherwood and P. Tindall, J. Am. Chem. SOC., 113
(1991) 2940; (c) D. Dubois, K. M. Kadish, S. Flanagan, and L. J. Wilson, J. Am.
Chem. SOC.,113 (1991) 7773; (d) Y.Ohsawa and T. Saji, J. Chem. Soc., Chem.
Commun., 1992, 781; (e) Q. Xie, E. Perez-Cordero, and L. Echegoyen, J. Am.
Chem. Soc., 114 (1992) 3978; ( f ) F. Zhou, C.Jehoulet, and A. J. Bard, J. Am. Chem.
Suc., 114 (1992) 11004.
2. M. S. Meier, T. F. Gum, J. P. Selegue and V. K. Vance, J. Chem. Soc.,Chem.
Commun., (1993) 63.
3. F. Wudl, Acc. Chem. Res., 25 (1992) 1667.
4. R. Taylor, J. Chem. Soc., Perkin Truns. 2, (1994) 2497.
5. Q.Li, F. Wudl, C. Thilgen, R. L. Whetten, and F. Diederich, J. Am. Chem. SOC.,114
(1992) 3996.
6. J. P.Selegue, J. P. Shaw, T. F. Guarr, and M. S. Meier, Recent Advances in the
Chemistry and Physics of Fullerenes, (The Electrochem. SOC.,)Eds. K. M. Kadish
and R. S. Ruoq 94-24 (1994) 1274.
7. S. A. Lerke, B. A. Parkinson, D. H. Evans, and P. J. Fagan, J. Am. Chem. Soc.,114
(1992) 5807.
8. D. J. Klein, T. G. Schmalz, T. G. Hite, and W. A Seitz, J. Am. Chem. Soc., 108
(1986) 1301; 110 (1988) 1113; R. Taylor, TetrahedronLett.,(1991) 3731; J. Chem.
Soc.,Perkin Trans. 2, (1992) 3.
9. P. A. Limbach, L. Schweikhard, K. A. Cowen, M. T. McDermott, A. G. Marshall,
and J. V. Coe, J. Am. Chem. Soc.,113 (1991) 6795.
10. L. S.Sunderlin, J. A. Paulino, J. Chow, B. Kahr,D. Ben-Amotz, and R. R., Squires,
J Am. Chem. SOC.,113 (1991) 5489.
11. A. Penicaud, J. Hsu, C.A. Reed, A. Koch, K. C. Khemani, P.-M. Allemand, and F.
Wudl, J. Am. Chem. Soc., 113 (1991) 6698.
12. J. Stinchcornbe, A. Ptinicaud, P. Bhyrappa, P. D. W. Boyd, and C. A. Reed, J. Am.
Chem. SOC.,114 (1992) 11004.
13. C. Bossard, S. Rigaut, D. Astruc, M. Delville, G. Feliz, A. Ftivrier-Bouvier, J.
201
The strong electrophilic character of the hllerene cages makes them extremely
susceptible towards both nucleophilic addition and substitution. Addition has been
carried out with both neutral and charged nucleophiles. The intermediate carbanions are
usually quenched with electrophilic species in order to obtain isolable products, so there
is some overlap of this work with that described in Chapter 11.
202
203
A similar predominence in the products was obtained in the reaction with dimethylamine,
and interestingly, the products here were found to be fluorescent.2
Figure 2 Possible sites for addition of twelve NR2H molecules to [6O]lllerene; the encircled and
thickened bonds npnsent two separateoctahedrally-locatedsets
The reaction With morpholine gives a product in which the hydrogens on the cage
have been shown to undergo hydrogen-deuterium exchange with MeOD, and this
provided an early demonstration of the acidity of cage-attached hydrogens, arising from
the strong electron Withdrawal by the cage.I The IH N M R signals for these protons
showed temperature dependence, which was interpreted in terms of their migration over
the cage surface ('globe trotting'). However, subsequent studies revealed that the NMR
results arose from temperature- and dilution-dependent hydrogen bonding interactions
with the water present in the solvent used for the N M R studies.3
Single electron transfer may be involved in the amination process (giving an
intermediateradical anion), ESR evidence for this being obtained in the case of reaction
of [6O@dferenewith ethyfenediamine and propyldne. 1 However, this was not the case
in the reaction with t-butylamine which would only take place in a polar solvent such as
dimethylf'ormamide.
Reaction of 42-diamines such as N,P-dimethyiethylenedidne, piperazine, or
homopipcrazine (Fig. 3: R*,R2 = Me, Me; (CH2)2; (CH2)3, respectively with
[60]lllerme gives rise to 1,2-addition of the amino groups in high yield (4570% on the
basis of fullerene used). A bis-adduct was also detected, and for reaction with piperazine
was separated by HPLC into six regioisomers.4
Reaction of [60]fullerene with tertiary amines, such as triethyia~nine,~
tetrakis(dimethylamino)ethylene,6 1,8-diazabicycl0[5,4,O]undec-7-ene,~ which do not
204
have a hydrogen to complete the normal addition, results in electron transfer to give salt-
like products.
1 ,Z-isomer 1,4-isomer
Figure 5 1,2- and 1,4-Derivativesof [6O]fullerene resulting from addition of aza crown ethers
205
addition of ten groups, and this has also been observed by Russian workers,1 Fig. 7
shows the mass spectrum of C ~ O ~ - B U ~ O ( C Oproduced
~ H ) ~ Oby reaction of [60]fkllerene
with n-butyllithium followed by C02 and hydrolysis. (NB. C02 is eliminated under
conditions of EI mass spectrometry and so does not appear in the spectrum). The
location of the ten addends has not been addressed previously, but given that there are
20 hexagons in [6O]fbllerene, addition across the high-order bond between pairs of
hexagons appears logical, as for example shown in the Schlegel diagram (inset, Fig. 7).
1109 1t'- x5.m
80
70
~ I
1111
1119
1136
Hgwe 7 Mass spectrum of the product of reaction of ifX]fuIlerene with n-BuLi/Cq, showing the
marked pttern of addition of 10 butyl groups. The Schtegel diagram shows possible locations
of addition sites between hexagon pairs.
206
Although the earlier work indicated that quenching with acids of the intermediate
carbanions formed by the addition of nucleophiles resulted in reformation of
[6O]fullerene, this conclusion may have arisen as a result of the tendency of the
derivatives to undergo elimination during mass spectrometry. In later work, in which
HPLC analysis was employed, reaction of f60]fullerene with equivalentsof either t-BuLi
or EtMgBr gave the corresponding monoadducts C 6 f l - B ~ and Get,
respectively.11 HPLC analysis indicated that other derivatives, arising from the
intermediates C60(f-Bu)#- (n = 2-6) could also be obtained.11 Other workers have
found that in the reaction of [60]fbllerene with t-BuLi, the intermediateanionic species
f-BuC60-Li+3-4THF and f-BuC6o-Li+4MeCN could be isolated, and that these also
gave c6oHr-B~on quenching with acid.12 As in the case of the addition of bulky azo
crown ethers, (see above) the bulk of the t-butyl addend here makes formation of the
1,Cisomer not wholly unfavourable compared to formation of the 1,2-isomer (cf. Fig. 5),
hence both are observed, though the former tended to rearrange into the latter.
Electrochemical experiments showed that that C6@-BU was 0.15 v harder to reduce
than [6O]hllerene itself12 and this arises from the electron supply to the cage by the
addends. The high electron withdrawal by the cage makes C6@-BU a very strong
carbon acid having a PKa of 5.7, with a weak (71 kcal mol-1) C-H bond dissoCiation
energy.
Extension of the method gave C6@-IXcompounds where X = octyl, but3-eny1,
1,3-dioxalan-2-yl, prop-2-yl, phenyl and tributylstannyl, and C7oHX compounds where
X = phenyl and methyl.13 The Cs symmetry of the latter compound showed that addition
had taken place across the 1,2-bond (see Chap. 1, Fig. 8 for numbering), though the
direction could not be ascertained. However, in the writers view, the hydrogen is
attached to C-2, i.e., to the polar pentagon. This reasoning is based on the fact that the
lH NMR shift, 6 6.04 is very close to that for the corresponding [6O]fullerene derivative
( 6 6.45).11 For dihydro[70]hllerene the lH NMR shifts for H-2 is ca. 0.9 ppm
downfield relative to that for H-1(ref. 14, note numbering change), and these values in
[70]hllerene are generally cu. 1 ppm upfield fiom those in [60]hllerene. This suggests
that the 6 value of 6.04 is too downfield to be assignable to H-1
Mononucleophilic addition has been achieved in the formation of
trimethylsilylethynyl derivatives of [60]hllerene (Fig. 8). 15916 Stability of the products
here may be enhanced by the high acidity of R.C=C.H compounds rendering elimination
of this group less favourable. Electron withdrawal by the MqSiC=C group makes the
reduction potentials more negative (by cu. 0.1 v) compared to [60]hllereneitself The
207
C-Si bond is exceptionally resistant to basecleavage, and this may arise &om repulsive
interactions between the (virtually orthogonal) p-orbitals of the cage and those of the
addend, resulting in increased pn-dz bonding to silicon.
[60]lllerene
-
i. Me3SiCSLi
ii. heat, toluene
iii. acid
CsCSiMej
3. Nucleophilic substitution
Thus far this has been studied far less than nucleophilic addition, but is likely to
become a growth area of lllerene chemistry as more of the precursors for nucleophilic
substitution become available.
Two early reports concerned the reaction of polychloro[X]fidlerenes (X = 60,
70) witrh methanoVKOH which gave a product showing a broad envelope of methoxy
groups at 6 ca. 3.7 in the I H NMR.23 Interestingly, FAB mass spectrometry indicated
the presence of 26 methoxy groups (cf. hydroxylation above), but no fbrther details have
been made available. Likewise, reaction of polyfluoxinated [60]lllerene was found to
undergo nucleophilic substitution by carbon-, oxygen-, and nitrogen nucleophiles, as well
as by hydride ion. The reaction rate decreased as more of the fluorines became replaced,
and a spectrum of reactivities was observed ranging from very high with reactive
nucleophiles such as amines, to slow with weak nucleophiles such as acetate ion.
Moreover, in the reaction with methoxidelmethanol, the product gave a pattern in the
1 H NMR similar to that noted aboveF4 and a similar pattern has also been noted from
the product of reaction of brominated [60]fhllerenes and C6oCl6 with sodium
methoxideJmethan01.2~
From qualitative experiments it appears that the reactivity rate decreases along
the series of halogenated hllerenes: (hal =) F > C1> Br and this parallels the reactivity of
halogenoaromatics towards nucleophilic substitution. Thus addition of the nucleophile
appears to be the kinetically most important step, rather than cleavage of the fillerene-
halogen bond. The mechanism of the elimination is presently open to speculation.
However, it is evident that a normal S N process
~ is geometrically impossible, and given
the very strong electron withdrawal by the cage, an sN1 mechanism is also ruled out.
Thus either a novel front-side attack is involved, or an addition-elimination process
occurs Figure 9; this has been proposed to account for the ready formation of epoxides
209
Nucleophilic substitution has been proposed as the step involved in the formation
of fiUarenols from nitrofullerene intermediates (see Chapter 5 ) , and likewise in the
formation of nitrohllerenols (having an average composition of 6-8 nitro groups and 7-
12 hydroxy groups per [6O]fillerene cage), from polynitr0[60]fullerenes.~~
Referenew
1. A. Hirsch, Q.Li, and F. Wudl, Angew. Chem. Zntl. Ecli. Engl., 30 (1991) 1339.
2. R.Sehradi, A. Govindaraj, R Nagarajan, T. Pradeep and C. N. R. Rao, Tetruhedion
Lett., (1992) 2069.
3. G.P. Miller, J. M. Millar, B. Liang, S. Uldrich, and J. E. Johnston, J. Chem. Soc.,
Chem. Comrnun.,(1993) 897.
4. K.Kampe, N. Egger, and M.Vogel, Angew. Chem. Zntl. &. Engl., 32 (1993)
1174.
5. J. Pol4 A. D. Darwish, R.A. Jackson, H. W. Kroto, M. F. Meidine, A. K. Abdul-
Sada, R. Taylor, and D. R. M.Walton, Fullerene Sci. and Technology, in press
(1 995).
6. P. W. Stephens, D. Cox, J. W. Lauher, L. Mihaly, J. B. Wiley, P. M. Allemand, A.
Hirach, K. Holczer, and G. Li, Nature, 355 (1992) 331; P. M. Allemand, K. C.
K h e , A. Koch, F. Wudl, K. Holczer, S. Donovan, G. Gruber, and J, D.
Thompson,Science, 253 (199 1) 30 1.
7. A. Skiebe, A. Hirsch, H. Klos, and B. Gotschy, Chem. Phys. Lett., 220 (1994) 138.
8. S.N.Davey, D. A. Leigh, A. E. Moody, L. W. Tetler, and F. A. Wade, J. Chem.
Soc.,Chem. Commun.,(1994) 397.
9. F. Wudl in Buckminsterfullerenes Eds. W. E. Billups and M. A. Ciufolini, VCH,
210
(1993)317.
10.P. Ya. Bayushkin, G. A. Domrachev, and V. L. Karnatsevich, personal
communication.
11. A. Hirsch, A. Soi, and H. R. Karfbnkel, Angew. Chem. I d . Eiin. Engl., 31 (1992)
766.
12.P.J. Fagan, P.J. Krusic, D. H. Evans, S. A. Lerke, and E. Johnston, J. Am. Chem.
Soc.,114 (1992)9697.
13.A. Hirsch, T. GrOsser, A Skiebe and A. Soi, Chem. Ber., 126 (1993)1061.
14.A.G.Avent, A. D. Darwish, D. K. Heimbach, H. W. Kroto, M. F. Meidine, J. P.
Parsons, C.Remars, R. Roers, 0. Ohashi, R.Taylor, and D. R.M. Walton, J. Chem.
Soc.,Perkin Trans. 2, (1994)15.
15.H. L. Anderson, R. Faust, Y. Rubin, aand F. Diederich, Angew. Chem. I d . MFZ.
Engl., 33 (1994)1366.
16.K.Komatsu, Y.Murata, N. Takimoto, S. Mori, N. Sugita, and T. S. M. Wan, J.
Org. Chem.,59 (1994)6101.
17.H.Nagashima, H.Terasaki, E. Kimura, K. Nakajima, and K. Itoh, J. Org. Chem., 59
(1994)1246.
18.S. Yamago, M. Yanagawa, and E. Nakamura, J. Chem. Soc.,Chem. Commun.,
( 1994)2093.
19.A Naim and P.B. Shevlin, Tetruhedron Left.,33 (1992)7097.
20.J. Li, A. Takeuchi, M. Ozawa, X. Li, K. Saigo, and K. Kitazawa, J. Chem. Soc.,
Chem. Commun., (1993)1784.
21.N. S. Schneider, A. D. Darwish, H. W. Kroto, R.Taylor, and D. R. M. Walton, J.
Chem. Soc.,Chem. Commun.,(1994)463.
22.S. R. Wilson and Y. Wu, J. Am. Chem. Sac.,115 (1993) 10334.
23.G.A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Sensharma, and
G. K. S. Prakash,J. Am. Chem. Sac.,113 (1991)9385.
24.R.Taylor, J. H. Holloway, E. G. Hope, A. G. Avent, G. J. Langley, T. J. Dennis, J.
P.Hare, H. W. Kroto, and D. R. M. Walton, J. Chem. Soc.,Chem. Commun.,(1992)
665.
25.P.R. Birkett, A. D. Darwish, H. W. Kroto, R. Taylor, and D. R. M. WaIton,
unpublished work.
26.R.Taylor, G.J. Langley, A. K.Brisdon, J. H. Holloway, E. G. Hope, H. W.Kroto,
and D. R.M. Walton, J. Chem. Sac.,Chem. Commun., (1993)874.
27.S. Roy and S. Sakar, J Chem. Soc.,Chem. Commun., (1994)275.
Chapter 13
Radical Additions to Fullerenes: Fullerenyl Radicals
Roger Taylor
211
212
Radicals containing up to 34 methyl groups attached to the cage have also been
formed, by irradiation of a benzene solution of [60]hllerene with di-1-butyl peroxide,l
and this seems to represent the upper limit for the numbers of groups of this size that can
be added. By contrast, photolysis or thermolysis of a mixture of dibenzoyl peroxide and
[60]fUlerene in benzene. showed the addition of up to 11 phenyl groups to the cage.5
The radical f-BuC60' has been subjected to considerable study and can be
generated in a number of ways e.g., by reaction of [6O]hllerene with di-t-butylmercury,
by irradiating [6O]fhllerene solutions with either t-butyl bromide, pivalaldehyde, or di-t-
butyl ketone, or by oxidation of c6oHt-B~with iodine in THF.697 The reverse of the
latter reaction can be obtained by reacting t-BuC60' with tri-n-butyltin hydride.6
The ESR signal intensity for the l-BuC60' radical showed an increme with
increasing temperature, the opposite of customary expectation? This was attributed to
the existence of the radicals as dimers, which dissociate on increasing the temperature.
Similar results were obtained for other radicals RC60' (R = i-Pr, adamantyi, CcI3,
CBr3) and the estimated bond strengths of the dimers showed a correlation with the size
of R. Since the spin density is located primarily at C2, C4, and C6, steric considerations
dicatate that the inter-cage bonding must be between the C4 cage atoms of the
participating radicals (Figure Z), rather than between the C2/6 sites.
Because of the eclipsmg interactions between the C-Me bonds of the t-butyl
group and the C 1-C2, C 1-C6, and C 1 4 9 bonds (see Figure 2) of the cage, free rotation
of the t-butyl group is hindered at low temperat~re.~ Likewise the lowest energy
conformer for the i-propyl group in i-PrC60. is as shown in Figure 3.* In EtC60* the
213
ethyl group adopts a non-symmetrical conformation (Figure 3),8 and this suggest that the
conformation-governing factor is location of the methyl groups over the hexagonal rings,
where there is more space.
It has been shown also that in a range of R3C60' alkyl radicals (including
H3C6oo), two of the R groups occupy equivalent positions, in parallel with the
structures shown in Figure 3.9 An interesting aspect of this work is that in an attempt to
form (CC13)3C6o0 radicals, the radical (CC13)2CIC6o0 (stable in the dark) was observed
instead, and also the new radical ClC60.; this latter may have relevance with regard to
the manner in which C6oC16 and C60Brg are formed (see Chapter 7).
Radicals have been formed between [60]fullerene and elements other than
carbon. For example, irradiation of a benzene solution of [6O]hllerene with MeSSMe
gave MeSC6oo, (and similarly EtSSEt gave EtSC6o0), but in contrast to the behaviour
of radicals with carbon addends described above, the ESR signal intensity here decreased
with increasing temperature,1 and may be associated with the weaker hllerene-S bond.
Calculationsindicated that the preferred conformation Of MeSC60' is that in which the
methyl group lies over the centre of a hexagon. Irradiation of benzene solution of
[60]firllercne with phenyl disulphide gave products C60Phx(SPh)yH,, indicating that in
this case both Pho and PhS' radicals attach to the cage.1 Alkoxy radicals also add to
the cage, as shown by irradiating benzene solutions of [60]fbllerene and either di-1-but1
peroxide or cumyl peroxide, whence 2-BuOC60' and Me2PhCOC6o0 were obtained.lo
Likewise use of bis(trifluoromethyl1) peroxide gave CF30C6o0,10
Phosphorus-containing radicals have also been prepared, e.g., (Me0)20PC6oo,
(Eto)20Pc6Oo$ and (i-Pr0)20PC6o0 (from e.g. irradiation of R2Hg precursors in
benzene solutions of [6O]hllerene. 1 Rates of dimerisation of the latter were determined
214
as 1.9 x 106 I mol-l s-1 at 0 OC, and five groups again added to the cage. Four types of
spin adducts were obtained for (i-Pr0)20PC6o0 (one of which was attributed to either
dimerisation of biradicals, or recombination of biradicals with a monoradical). 12 The
remaining three adducts were attributed13 (in the case of addition of (Me0)20PC6Oo)
to the structures shown in Figure. 4, with addition at the a and c carbons (notation as
given in ref. 14).
Radicals with boron attached to the cage in the form of the m-B1$9C2H2-
carboranyl group have been obtained, and these provide an interesting unison of the two
cage systems, as shown in Figure 5.15 The dimerisation rate coefficient was ca. 1 x lo6
I mol-l s-l at 27 OC.
The ESR spectra have been obtained for the radicals (which are somewhat
unstable) firmed by addition of either Pd(F'Ph3)z or Pt(PPh3)z to (R0)20PC6oo. q2 -
addition of Pt(PPh3)4 to [ ( R O ~ O P C ~ O gives
] ~ derivatives which dissociate to the
monom& radicals (Ro)20P.Pt(PPh3)2C6o0when exposed to visible light. In these
species, the Pt(PPh3)z group is located in different positions relative to the radical
centre, and five distinct ESR signals are obtained.16
Rhenium-containing radicals (CO)5Re0, produced either by photodissociation of
Re(C))Io, or by reaction of ($-Ph$)Re(C))4 with CO (which displaces PPh3C)
combine with [60]lllerene to give c6O[Re(CO)5]2, in what is believed to have a 1,4-
addition pattern. This product is unstable and decomposes through (C0)5ReC6o0 as a
probable intermediate.17
Three isomers of r-BuC70. have been observed, having g values of 2.00271,
2.00248, and 2.00210, with corresponding hyperfine interactions with the C-atom
attached to the cage of 14.2, 11.3, and 13.8 G.18 Likewise three isomers were observed
for fomtion of radicals C13CC7o0 (34.6,30.5, and 26.7 G) and (MeO)2OPC7oo (71.2,
66.8, and 55.9 G). For the t-butyl radical, only the isomer ofg 2.0021 (13.8 G) showed
hyperfifie interactionswith the carbons orrho and puru to the radical centre (cf.Figure 2)
comparable to those observed in t-BUC60'. On the basis that only the structure of the
end cap of [70]fiJlereneparallels that in [60]fullerene, and moreover that this radical was
the only one to show an increased ESR sigd with increasing temperature (indicating
dimeridon), it was concluded that the r-butyl group was attached to C2 (or u carbon)
(see Figures 8 and 23, Chap. 1 for nomenclature), with the radical centred on C1 (b-
&n)(cfFig. 4c). Given that this addition takes place across what is usually the most
reactive bond in [7O]fhllerene, it is conceivable that it could occur in the reverse
direction. The structures of the other radical could not be identified, and this is an area
worthy of firther work, in view of the growing body of interesting detail concerning the
reactivity of [7O]fi.1llerene that is beginning to emerge from other studies.
Further work has also been carried out on fluorine-containing radicals, viz.
F$C60', (F3C)F2CCC60r (F~C)~FCCC~O.,and ( F ~ C ) ~ C C C ~ OThe '.~~
conformations of the first two radicals are symmetrical as shown in Figure 6 (F3CC60'
has a barrier to rotation of 7 kcal mol-I). However, the ( F ~ C ) ~ F C C C ~radical
O * adopts
an asymmetrical conformation having a barrier between the two enantiomers (one is
shown in Figure 6) of 3.5 kcal mol-I. It is surprisingthat the bulkier CF3 groups prefer
to lie over a pentagon which is also more electron-deficient than a hexagon. There are
evidently complex factors here which are as yet poorly understood. For the radical
(F3C)3CCC6o0 the average conformation is the symmetrical one (Figure 6) but the CF3
groups rotate in synchrony with rotation about the C-C60 bond.
Perfluorodkylated fidlerenes have been produced by two research groups. One
technique involved the reaction of the fkllerene with peduoroalkyi fie-radicals
produced by either thermal or photochemical decomposition of precursors such as
fluoroalkyl iodides or fluorodiacyl peroxides, RdCO)OO(CO)Rf .20 For example,
heating a solution of [60]fUllerene with perfluorohexyl iodide in 1,2,4-trichlorobenzene
produced a product having between 6 and 12 (mainly 10) perfluoroalkyl groups attached
to the cage, though it also contained some hydrogen through radical abstraction from the
solvent. Similarly, photochemical irradiation of a solution of trifluoromethyl iodide in
benzene produced the addition of up to 13 CF3 groups to the cage, though again some
hydrogen was incorporated from the solvent. To avoid hydrogen abstractionthe reaction
was repeated using hexduorobenzene as a solvent and here up to 14 CF3 groups alone
were attached to [6O]lllerene. Up to 16 perfluoroethyl groups could be attached to the
cage by using perfluoropropionyl peroxide in Freon 113 solution at -6 O C .
An alternative procedure used trifluoromethyl iodide and copper and produced
from each fullerene, a hexane-soluble fraction and an insoluble one. The former consisted
of fiillerenes with up to 16 CF3 groups attached to [6O]fbllerene and 18 to [70]fbUerene
Figure 7a,b. The insoluble materials gave very similar mass spectra to these, but were
much less volatile and were shown by IR and by reaction with acyl halide, to contain a
number of hydroxy groups; these do not show under EI mass spectrometric
conditions21 A very notable feature about the polyfluoroalkyl derivativesis that they are
very volatile, can be sublimed readily, are thermally stable up to 270 O C , and are stable
towards both sulphuric acid and sodium hydroxide Bis(trifluoromethy1)nitroxide radicals
[(CF3)2NOo]react with [60]fillereneto give the product C60[(CF3)2NO],, n = 18 on
average 22
217
in 1 in
5, %.
S. s.
m. m
. a
%.
m.
0.
6.
a.
a.
T I
I: I
P. P.
8. $5.
9. 9.
6. (I.
a. U
31.
I.
a.
a.
13.
la.
I.
*a
Figure 74b. Mass s p t m of the products of reaction of [60]- and [70]fullerene with CF3I/Cu. Inserts
show epectra for the corresponding hydroxyantahhg derivatives (seetext).
References
1. P. J. Krusic, E.Wasserman, P.N. Keizer, J. R. Morton, and K. F. Preston, Science,
254 (1991) 1183.
2. R. Tiylor, Tetrahedon Lett., (1991) 3734; Phil. Trans. R. Soc. hna! A 343 (1993)
87.
3. R. Taylor, EfectrophilicAromatic Substittrtion, Wiiey, 1989, pp 15-18.
218
Alan L. Balch
Deparjment of Chemistry
University of California, Davis
Davis, California 95616 USA
1. Introduction
This chapter is concerned with metal-fullerenederivatives that have been isolated in
macrOScOpic quantities. lsolation of these materials in milligram quantitiesmakes analysis
by a variety of spectroscopic techniques and structural analysis by X-ray diffraction
feasible. Such studies are a natural outcome of the discovery of techniques for the
preparation of macroscopic quantitiesof the fullerenesthemselves.**2The fullereneshave
both an outside and an inside surface available for binding to metal atoms and metal
complexes. Obviously, the external surface is more readily accessible to reaction with
conventional coordination complexes and organometallic compounds. As a consequence,
significant advances have been made on the preparation and characterization of these
exohedral complexes. The external surfaces of all of the fullexenespresent arrays of five-
and six-membered rings. Consequently it was appealing to consider that the fullerenes
would form organometalliccomplexes analogous to the numerous @-benzene and 115-
cyclopentadiene compounds that are so prevalent in the organometallic literature.
However, the reactivity of the fuIlercnes that have been isolated shows that they react
primarily as olefms, especially as electron-deficientolefms, and not as typical aromatic
hydrocarbons? Thus dihapto coordination, rather than poly-hapto coordination, to a single
metal center has been obsexved in the exohcdral complexes that have been thoroughly
Charactcri?;ed
The possibility of obtaining compounds with metal atoms inside fullerenes, the
endoh& compounds, was recognized very early in the examination of fullercne-derived
species? However, progress in isolating macr#scupic amounts of these in purified form
220
221
has been slower than the preparation of the exohedral complexes. Consequently the
concluding scction. which is devoted to isolated endohedral complexes,is short.
2 . Additions to C6o
While all of the carbon atoms in & are equivalent by symmetry, there are two
distinct bond types as s e n in Figure 1. Structural and theoretical studies have shown that
the C-C bonds at 6:6 ring junctions arc shorter than those at the 6 5 ring juncti~ns.s-~ A
single erystal X-ray diffraction study of at 110 K gives the 6 6 bond length of 1.387(3)
A and the 6 5 bond length of 1.450(3) A.5 In the reactions of Cja with metal complexes,
so far, the pndominant reaction has involved addition to the n-bond at a 6:6 ring junction.
Because of the highly symmetrical nature of Cja with its 30 individual 6 6 ring junctions,
there is considerable propensity toward multiple additions and the creation of mixtures with
varying levels of addition. Nevertheless procedures for the preparation of pure single
addition products have been developed and proven to give important information in regard
to the structure and chemical reactivity of these carbon clusters. Isolation of some pure
multiple addition products, especially double addition products has also been
accomplished. For double addition, eight regio isomers can form if nactivity is confined to
6 6 ring junctions. Figure 1 outlines the slxucturcs of these. If the first addition occurs at
the arrow,then eight regio isomers can be identified by the numbers 1-8. Of these isomers
one has Dul symmetry, three have C2 symmetry, and four have Cssymmetry if the added
groups have at least CzVsymmetry themselves.
I Maximum
t Site Symmetry
8 C'
7 C'
6 c,
5 c,
4 C'
3 c,
2 c,
1 D2h
Figure 1. MI,the structure of c60. Righk sites for double addition to Ca. The initial addition occurs
at the m w and Ihe numbers identify pmible redo isomus.
222
2.1 Osmylation
Osmium tetroxide is a powerful oxidant which is useful in converting oldins into
diols by means of intermediate osmate esters.8 Osmium tetroxide in the presence of
pyridine dso forms stable addum with polycyclic ammatic hydrocarbons.9 Depenblng on
the stoichiomtry. m m n t of & with osmium tetroxide and pyridine by) yields either
the single addition product, c+joO2OsO2(py)2. and/or a mixture of five double addition
} 2shown in Figure 2.1@*4The single addition pmducthas
products, ~ ( 0 2 0 ~ 0 2 ( p y ) 2as
been separated from the others, because it has significantly higher solubility in toluene.
Exchange of the pyridhe ligands for 4-t-butylpyridhe gave a more solubie derivativethat
was crystallizedand sa~dicdby singlecrystal X-ray diffraction, A drawing of the smw
of this adduct, C60020~02(4-r-butylpyridine)2.2.5 toluene, is shown in Figure 3. The
osmyl group is connected to the fullacne by two oxygen atoms which have added m s s
the C-C bond at a 6 6 ring fusion. This st~cturchas special significancesince it was the
fmt crystallographic demonstration that the & moiety possessed the soccer ball spuchne
which had been proposed in 1985.1s Osmylation producesonly a local pertubadon to the
fullercne core. The trimordinate atoms of this moiety lie in a shell with a radius of 3.46 to
3.56 A about the center with an average center-to-carbon distance of 3.512 A. The
oxygen-bound carbon atoms, however, lie 3.80(2) and 3.81 (A) away from the center.
The 13C N M R spectrum of 13C enriched Q0020~02(r-Bupy)2 has been
thoroughly analyzed and the connectivities determined from a 2D N M R INADEQUATE
experiment.14 The chemical shifts and coupling constants for the seventeen different types
of carbon ntom in the QJ portion of the molecule arc given in Table I. The tetracoordinate
carbons produce a resonande that is well upfield of the resonances of the tricoordinate
carbon atoms. The shifts for these carbon atoms lie in the 137-153 pprn range. (For C a
itself a single resonance at 142.68 ppm is observed). While the chemical shifts within the
137-153 ppm do not show a well defined pattern that correlates with structure, the C-C
coupling constants do follow such a pattern. C-C coupling constants in the range 54-57 Hz
correspond to bonds at 5:6 ring junctions, coupling constants in the 65-71 Hz range
cornspond to bonds at 6% ring junctions while a unique 48 Hz coupling constant is found
for the bond at the 6 5 ring junctions which involve the oxygenated carbon atoms.
Molecular orbital calculation have been obtained for &020s@(py)2.16 These
show that the states near the frontier are not affected by the osmylation and that the bonding
interactionslie lower in energy. However, the HOMO-LUMO gap in the adduct is reduced
relative to G j o itself by the presence of non-bonding orbitals that are centered on the
osmium fragment.
Figure 3. Ihe structure. of C6oo2os@(r-Bupyh as determinedby X-ray diffraction (from ref. 11).
224
broaduil in this region of the CD sptctnun. The CD spectra of resolved forms of isomer
2 showr distinct, but similarly rich features, in the 500-800 nm region. The
enandorelectivityin the bis-osmylationprocess has baen attributed to attractiveelectronic
interdons &tween osmium ligands and the fullmnes mhcr than repulsive, stcric effects.
As we shall see later in this chapter, t h m is ample crystallographic evidence for attractive
intarcdonsbetween aromatic gmaps and fulluene surfaces.
I
u# WK) u# mo arm
trwn 4. clrcufrr dichorism p m of (+) and (-) forms of bi.osmytntion products of % (fmm ref.
18).
large, olefin replaces another. The structure of the complex, as detedned by single
crystal X-ray difhction, is shown in Figure 5.21 The overall structure resembles that of
the precursor (PhgP)2Pt(q2-C2H4).26 The C(l)-C(2)distance (1.502(30) A) is
considerably longer than the average C-Cdistance at unperturbed 6 6 ring junctions
226
(1.388(30) A). The platinum carbon distances. 2.145(2.1) and 2.115(23) A, are similar to
those, 2.106(4) and 2.1 16(9) A. found in the ethylene adduct, (PhsP)zPt(q2-C2H& The
carbon atoms to which the platinum atom is bound are pulled out from the corc of the
fullaene. In metal olefm complexes, it is ncognized that the olefinic carbon atoms bacome
pyramidalized when they are coordinated to a metal center. In this regard, the curved,
rather than planar, nature of the fulerene surface makes it an attractive candidate for the
formation of transition metal X-adducts. However, the fact that the carbon atoms that are
bound to platinum are pulled out from the cluster core reflects the fact that further
pyramidalization is required to accommodate metal bonding.
The green complex (~$C+jo)Pt(PPh3)2 is sufficiently soluble in tetrahydrofurrnto
obtain 31P NMR spectral data?* The spectrum consists of a singlet at 6 27.0 ppm with
satellites due to coupling to 19% with J (Pt, P) of 3936 Hz. For comparison, the 31P
NMR spectnun of (Ph3P)2Pt($-C2Hq) consists of a similar resonance with 6 38.4 ppm
and J (Pt, P)of 3738 Hz.
Similar complexes with nickel, palladium, and platinum can also be obtained by
reaction of with M(PR3)4via eq. Z . z s The structure of the palladiumcomplex
E l a c t r o c ~ c astudies
l on these platinum adducts nveal fullmne basad reductions
with enharrced lability of the anionic fonns.3 The electrochemical behavior of (q2-
C!&%(lTb3h and Ctjo me COmpBnd in the cyclic voltmmogmm seen in Figure 8. Three
reduction waves (Mlc. M ~ c M3c) , arc ascribed to the electrochemically reversible
formation of t($-Cao)Pt(PPh3)21-, [(q2-C60)Pt(PPh3)212-and I($-%)Pt(PPh3)213-
rcspccdvely. With r c g d to Q itself, reduction of the platinum adduct is shifted by a.
0.3 V to m ~negative t potentials for each of the thrte reduction steps. The voltammognun
in Figura 9 shows that some fne Qo is present at the outset of the experiment and that its
concanardon grows as the sample is reduced. It was concluded that the reduced forms am
susceptible to facile d i d a t i o n of the Pt(PPh3h unit and the fulleride ion. The rates of
dissociulon have been examined for a variety of related complexes. ($-&)M(PR3)2, and
it has bcen shown that the rate depends on the ligand (faster for PPh3 than PEtj), the metal
(faster for Ni than Pd and Pd than Pt)and the degree of reduction (faster for the trianion,
slowest for the monoanion). Reduction potentials for the series of adducts
(&)(Pt(PEt3h)n. with n = 1 to 4, show a 0.36 V cathodic shift for each addad metal for
the inidd reduction that produces a monoanion. The fact that the three adducts ($-
Qo)M(PEt3)2,with M = Ni, Pd, and Pt,arc reduced at the same potential has been taken
to idcatc that backdonation of d electron density to the fullerme is rclativcly localized.
"he Raman spectra of these platinum and palladium adducts show the symmetry
lowering effects of addition to the fukrcne.~whereas & itseu has 10 vibrations (of the
possible 174 modes) that arc Raman active. the adducts show morc complex spccea
I I I I I I I I I I
-.a -1.0 -l.b -1 8 -2 2
E vs. Fc'l' I V
Figure 8' Cyclic voltammograms at a platinum disk of (q2-C60)Pt(PPh3)2 (A) and C&I (B) h
tceahydrohnanwith ( n - B m d 88 supporting elecaolyte(hnfaence24).
230
A-
*
6 .A
231
the metal complex; no ligands arc displaced from the iridium in the process. Similar
rtactiaapof vws coapkx w ith electron deficient olefins were previously described31
Brown black crystals of (tlz-c6o)Ir(CO)a(PPh3)2.5csHghave been obtained by
diffusia of concentrated benzene solutions of the reactants.30 nte smcture ofthe adduct
is shown in Figure 10. The iridium is bound to a 6 6 ring junction, and the (q2-
Q0)hfPPhjhportion ofthe molecule closely resembles ($-C,y-~)Pd(PPh3)2 (Elgun5).
Tht electronic structure of (q~&)Ir(CO)Cl(PPh3h has been probed by i n M 3
and Mchobauer spcctroscopy.32 In the infiwd, Vaska noted that oxidative-additions to
It(CO)C1(PPhgh resulted in an increase in the CO stretching frequency and that the
magnitude of that increase correlated with thc rcvmibility of the addition.33 k r (112-
Ca)Ir(CO)Cl(PPh3)2 that increase (from 1953 cm-1 in the parent to 2014 cm-1 in the
fullmnc adduct) cornsponds to cases of easily revemible addition. That change is
232
consistent with the solution behavior of the adduct which is largely dissociated into its
components. & and Ir(CO)Cl(PPh3)2. in dichloromethane solution. It is also noteworthy
that the tetracyanoethylene (TCNEi) adduct, (q2-TCNE)Ir(CO)Cl(PPh3)2,and the
tetrafluoroethyleneadduct (rl2-CzF4)Ir(cO)Cl(Ph3)2, show a larger increasein the CO
stretching frequency (to 2052 and 2057 cm-1~espeCtively).33Thus Q is less effective in
withdrawing d-eltctrondensity from iridium than axe these highly e l m n deficient olefins.
The changes in the Mtissbauer spectraof these Compounds has been analyzed situilarly?2
The d m a s e in the quadrupolar splitting on adduct formation (from 6.52(3) mm/s for the
patent to 2.714(15) mm/s for the Cjo adduct) and 1.837(15) mm/s for the TCNE adduct)
has been ascribed to redistribution of d electrons and increasing electron withdrawal by
TCNE relative to C60. The changes in the isomer shifts (0.022(1) mm/s for
Ir(CO)Cl(PPh3)2 (-0.194(10) for the TCNE adduct, and -0.259(10) for the C,~Jadduct).
indicate a dacrease in s electron density upon adduct formation.
The fullerene moiety is so weakly bound in (qzC&$r(CO)Cl(Ph3)2 that it readily
dissociates in solution. Consequently the usual NMR spectroscopic techniques that are
useful in solution characterization of metal complexes have been of little help in studying
the fullerene adducts of Vaska's complex. However, this ease of dissociation and
reassociation has a great advantage in that it facilitates the preparation of crystalline
derivatives that an suitable for single crystal X-raydiffraction. Thus as seen lam in this
chapter, adduct formation with lr(CO)Cl(PPh3)2 and related complexes has become a
useful tool to gain valuable information about the structure and sites of chemical reactivity
in higher fullemes and in &C derivatives.
The structures of both (q2-C60)Ir(CO)C1(PPhs)z (Figure 10) and (q2-
O)Pd(PPh3)2 (Figure 5 ) show that two of the phenyl rings of the triphenylphosphine
ligands lie over the fullerene surface where they make face-to-face, YC-X contact.
Additionally, in the iridium adduct there is a veritable river of benzene molecules that run
through the structure. The locations of these solvate molecules in the solid are shown in
the view of the unit cell shown in Figure 11. These solvate molecules f i l what would
otherwise be voids in the structure and make z-z contacts with the fullerene portion and
with one another. The presence of such solvate molecules within crystalline
metallofullerenesand of fderenes themselves is extnrordinarily common.%-%
The face-to-face contact between one phenyl group of each triphenylphosphine
ligand in (q2-C60)Ir(CO)Cl(PPh3)2suggested that it should be possible to design new
phosphine ligands which would enhance such contacts. To do this, it was apparent that a
233
curved substituent that incorporated flat, aromatic surfaces linked by flexible connectors
that would allow the aromatic portions to wrap around the fullerene would be desirable.
Consequently, the new ligand Ph2FCI-&H4OCH2C& (PhZpbob) was synthesized and
converted into Ir(CO)Cl(Ph2Pbob)2.37 This Vaska-type complex reacts with &Ito form
(q2-~)Ir(CO)Cl(Ph2Pbob)zwhich precipitates from benzene solution as black crystals.
While the fullercne is bound to iridium in a normal ~2 fashion at a 6 6 ring junction, this
solid has several remarkable features. No benzene is incorporated into the solid, it
crystallizesas a solvate-free species. Two benzyloxybenzyl p u p s of one molecule of the
complex encircle the c60 moiety of the adjacent molecule in what Marilyn Olmstepd has
called a "gentle van der Waals embrace". Figure 12 shows a drawing of an isolated
molecule while Figure 13 shows portion of the infmite chain of such molecules with one
embracing the next in a linear array that resembles elephants in a hunk-to-tail formation.
The solid is extraordinarilyefficiently packed. Two of the phenyl rings of the Phsbob
ligand make face-to-face TI contact with the fullerene, while the other two fit snugly
between two columns of this van der Waals polymer. While Ir(CO)Cl(Ph2Pbob)2m d l y
forms a crystallinesolid with %,none is formed with Cm. pmumably because the larger
fullenme does not fit into such a compact structure as that shown in Figure 14.
The reactivity of Vaska's complex may be modulated by changing the ligands that
arc present Alkyl phosphines produce complexes that are more prone to oxidative-addition
than complexes with aryl phosphine ligands. For example, oxidative addition to
Ir(CO)Cl(PMe2Ph)2 is about 200 times larger than that for Ir(CO)Cl(PPh3)2.38 This type
of ligand modification has been exploited as a means toward obtaining multiple addition
products of c60. Reactions of (&with excess (2 to 12 fold) of Ir(CO)Cl(PMe2Ph)2?9
Ir(CO)Cl(PEt3)24 or I ~ ( C O ) C I ( P B Uhas ~ ~lead
) ~ ~to crystallization of double addition
products. In each case the pattern of addition is the same; the double addition product
crystallizesas the 1orpara isomer shown in Figure 2. Statistically,this is the isamer with
the lowest probability for formation, but it is also the isomer with the highest possible
symmetry and probably the most compact structure. The reaction of C6o with
Ir(CO)Cl(PMe2Ph)2is complex in that at least four different types of solids have been
idcntified.39 Two crystallineforms of the double addition product have been examincd by
X-ray diffraction, and the structures are shown in Figure 15. The adducts vary in s6lvate
composition and in the orientation of the substituentson the phosphine ligands. but both
have the para orientation of the two iridium complexes. The geometry within the form
which crystallizes as obelisks, has the four phenyl rings of the phosphine ligands oriented
235
so that they make face-to-face contact with the fullerene. In the other, plate-forming
modlllcation, the phenyl subtituents all face away from the fullercne core so that they
interact mon directly with one another than with the Qo portion. However, this solid bas
anothcr inmesting ame-fuUenne contact. Two benzene mlecule~that cocrystallizewith
the adduct molecule arc oriented nearly perpendicular to the fullerene surface. These
benzene mlccules arc unngcd so that H(49) lies 3.09 A fromthe electron-rich. 6:6 ring
junctioa that involves C(16) and C(26). Such edge-to-surfaceinteractions are recognized
as attractive contributions in the energetic properties of crystalline arenes?14 Figure 15
shows ths m t u r c Of motha Such pm-adduct, C60(11fCO)cl(rnt3h)~.~
236
product of this sort. Figure 16 shows its structure as determined by single crystal X-ray
diffraction.& While the two fullerene units are covalently linked through the mctnllo-
macmcycle, the fdmne center-to-center sejwation is quite large, 16.559 A, and so is the
non-bonded Ir.41 distance, 8.104 A.
237
The reaction of fullmne derivatives with Vaska's compound can also produce
a y s t d l h mataialsthat give information about their smctm and nactivity. The fulkrene
epoxide, Qjo0,47*48 reacts with Ir(CO)Cl(PPh3)2 to form black crystals of (q*-
W)k(CO)Cl(PPhsk.49 The StnrCtuFe of the adduct. & W dby X-ray diffraction,
is shown in F i m 17. The cpoxide functionality is clearly present. The O(1)(3)-C(4)
unit famu a nearly equilateral piangle; and the C-0 distances(1.445(12), 1.46312) A) and
C-C dirruKx (1.480(11) A) arc within the range of distancesexpected for an epoxide unit.
Surprisingly, in the context of all the double addition p d u c t s described above, the
additioa occurs 80 that the iridium complex binds to a 6 6 ring junction that shares a
conxmn hexagonal face with the epoxide u n i ~The non-bonded I r - q l ) separation is large
(3.463(7) A), and it is clear that thm is no direct interaction of the iridium and oxygen,
This is psrticularly significant since there arc cases known where low-valent metal
complcms do insert into the C-0 bonds of epoxides.50 As is fnquently the case with
fulleawfecOmpOunds the s t r u c m is not fuUy odemi but it is considerably less disordered
than cryrUlline &O itsclf.51 In the d i d state. the epoxide oxygen atom occupies two
s i w (ql)and O(1')) with diffwnt occupancies,but both sites are similarly situated with
rcgrrd do theplacantnt of the iridium.
atoms that cross link two chains. A second type of palladium atom that merely sits on the
fullcrene surface may also be present. Heating solid C j r ~ H in
1 toluene results in the partial
dissolutionof h, and the formation of a solid with a Pd/cao ratio between 2 and 3.
Q@dn with n > 2.8 is a catalyst for hydrogenation of acetylenes and olefins at
room temporam.61 Because polymers with lower Pd/& ratios are inactive as catalysts,
it has been suggested that the exposed surface palladium atoms, rather than the buried,
cro88 linking palladium atoms, arc involved in this process. Further physical and structural
-
Charactcnzationofthispdymersppearswarranted.
results from addition of two *Re(CO)sradicals to the fullmne. Numerous examplesof the
addition of organic radicals to Qo are known.64 ~ h same c product can dso be formed
h m the reaction of a with ($-Ph3C)Re(CO)4 in the presence of carbon monoxide.
Under these conditions *Re(CO)sis known to be fonmd. C&O(Rc(CO)5)2is unstable in
solution and decays in a first order process back to and Re2(C0)10. The rdduct
C&O(Re(CO)5)2is believed to have the two organomctallic fhgments attached at opposite
ends of a hexagonal face of the fuilerene via 1,4 addition as shown in Figure 20. This
bonding mode is novel among organometallics because it is the first apparent example of Q
rather than IE attachment of a metal center to
fullmnc absorption from 330 to 339 which is indicative of one-electron reduction. The
magnedc Nsceptibilty of the solid shows Curie-Weiss behavia with a room temperatun
moment of 4,2(1)p~.The expected moment for a non-interacting S = 3/2. It2 system is.
4.27 WB. In THF solution the complex behaves as a 1:1 electrolyte. but in toluene solution
back elaxma uansfer occul~lto give a so~ution of c r 4 T P P ) and neutral c60.
The reduction potentialof cobdtooene ( 4 9 8 V vs. SCE)is such that it is capable
of causingeither one or two electron ~eductionof &69*m Addition of cottaltoccne to ~ 6 0
in 1:1 ratio in benmnitrile solution yields brown [(rl5-C5Hs)2Co+](C60-)*PhCN.69
~ d d i d o nof excess cobaltooene is reported to generate the dianion, (&2-).69 The epr
spectrum of [(qs-CsH~hCo+l(Qo-).PhCN in tctrahydmfuran shows a resonance at g =
1.9969 with a temperature dependent linewidth (7 G at 4.5 K. 24 G at 130 K).
Additionally, the material shows a sharp spike of low intensity at g = 2.000. Read and
coworkerr suggest that the spike arises from t h d population of an excited statc that
could result from splitting of the degeneracy of the qustate. Reductionwas suggested to
caw a &onion from b to Ds symmetry that would split the qustate into2Ah and2E1,
states.@ However, the absence of this spike in other salts raises the possibility that the
s p bm ts from Species Other than (*).
Ttaatmcnt of Qo with excess cobaltocene in carbon disulfide produces black
crystals of [(~~-C~S~CO+](Q~-).CSZ that were bartly suitable for X-ray dithction.70
A view of molecule packing of the components is given in R g m 2 1. The anion
P
244
shows orientational disorder with two different orientations resolved. Unfortunately, the
poor crystal quality and the disorder do not allow a meaningfd analysis ofthe effect of
reduction on the geometry of the fulleride component. The dimensions of the cobalt corn-
plex, however, me consistent with the pnsence of the cobaiticiniurn ion rather than neutral
cobaltocene. The epr spectrum, with a narrow line at g = 1.998, which broadens on
wanning, is indicative of elccrron transfer to give the fulleride ion. The epr spccmm at 4
K does not show the known features of neutral cobaltocene, n a does it show evidence of a
namw spike at higher tempratures.
The electron-reservoir complex, ((q%!5Hs)FeI(q6-C&qj) 1, is an even stronger
-
reductant (Eln 1.55 V vs. SCE in dimethylfoxmamide) than cobaltocc11e.7~Consequent-
ly it should be capable of effwting reduction of %through three steps eventually to form
the trianion, &3-. Indeed, titration of Qo with ((~$-CsHs)FeI(q6-QMeg)) produces
rhree dark brown, paramagnetic, air sensitive salts: [(qs-C~Hs)Fen(116-CM~)+lo.
[(rls-CsHs)Fen(116-CsMe6)+12(C602-), and [(r15-CSHs)Fen(r16-CMe6)+13(C603-).72 A
sharp, symmetrical epr line was observed at g = 2.0020 for the salts that contained (&-)
(linewidth 2.6 0)and (C&-) (linewidth 4.0 G ) at 300 K. For [(qS-CsH5)Fe~(q6-
C6Me6)+]3(Ctjo3-)however,
, the resonance at g = 2.0040 exhibited a linewidth that
dropped markedly with ternpcraturefrom46G at 30 K m 6 G at 4 K.
T
246
unit cell down the a axis. The geometrical features of the individual componentsdo not
show any significant variation from their n d structurts. The fullerem is ordend in this
solid. Three of the four cyclopcntadienylrings of the organomtallic complex BTC involved
in face-to-face. IC-IC interactions with adjacent 0molecules. The orientations of these and
some dimensions within the triad of Gjrj molecules an also given in Figure 23. The
infrared spectrum of the solid shows a slight shift in v(C0) for the iron cluster (from1626
cm for ( F ~ ( C O ) ~ ( ~ S - C ~to S ) ~ )cm-l in the ternary cocrystals). This shift is
H 1640
consistent with a weak donor function for the organometailic component
Attempts to coordinate PdClz units onto Gjo through reaction with the txakmcly
labile complex, (PhCN)2PdC12, in benzene solution have resulted in the formation of
another ternary material: Cao.2(P&C112).2.5Qj&74 A view of the unit cell is shown in
Figure 24. The P&C112 cluster, which has dimensions similar to that of ( trans
Cl-Cl distance, 6.54 A; trans Pd***Pddistance, 4.67 A), forms by a spontaneous, self-
association process. Benzene rings arc intersperstd between the fullmne and the Pdgc112
clusters. There appears to be a strong attraction between (PQCl12)and conventional,flat
aromatic molecules.7S since a variety of binary cocrystals of Pic112 with aromatic
molecules (benzene, hexamethylbenzene.and mcsitylene) have been preparcd.74
247
5 . Additions to C70
The structural complexity of the fullennes increases as their size inrreases.76*77
With Qo, the second most abundant fullmne in standard preparations, there are five types
of carbon atoms and eight distinct types of bonds.2 These can be visualized by turning to
Figure 25. The five types of carbon atoms are anangd in parallel layers, a feature which
is uaiqu~to this fulleme. If addition is confmd to 6 6 ringjunctions. then that arc four
possible single addition proaucts that can be anticipated to form upon additions to C70.
The mults of H k k d molecular orbital calculationarc included in Figure 25.77 The
1 9 aad 7.8 C-C bonds at the 6 6 ring junctions at the poles of the molecule have the
highest x bond &and an expected to be the most lcBctive by that criterion.
5 .I A&n of Ir(CO)Cl(PR3)2
The formation Of the adduct ( ~ 2 - c ~ ~ ) ~ ( c o ) ~ ~ ( Pthrough P h ~the )~~2.~c~
xeacdo6 of Ir(CO)Cl(PPhgh with C70 gave a crystalline matcrial that produced the first
detailed pmetric picture of any fulleEne larger than Qo.78 Figure 26 shows a view of
the m o W that was obtainedfrom a single crystal X-ray study. Despite the possibility of
f w g a variety of ngio isomers, only one crystalline compound is formed. It has the
iridimtuamc a d h a t 4 to a 1.9 C-C bond type (at a 6:6ringjunction) at one pole of the
molecule. The con structure of the fullmne conforms to expectation. It possesses an
ellipeoidrl shape with a 7.90 A distance dong the long axis and a 6.82 A diameter. Notice
that the a m a m of the mlcculc is highest at the poles, whik the hexagons about the waist
of the molecule arc actually concave. The C-C bond distances from that structure arc
ComPIped in Table 11to those of C 7 0 - 6 ( S 8 ) , ~to ~ . those
~ of a nlatcd double addition
product.81 and to those h m a theoretical calculation.82 These data arc a l l consistent with
one another, and they indicate that complex formation causes only a local structural
ddonnadon of the carbon cage. The redetermination of the structure in the C70 /S8
cocryst&,0 however, gives the most accurate C C distances.
'IYw hlation of only one isomer of(q2-C7r$rOO)Cl(PPh3)2 can be attributed to the
r c v d W t y of the simple addition naction that is involved in its fonnation. The formation
of thfr particular isomer ~eflcctsboth the high R b o n d d e r of the 1.9 bond, and the fact
that tlm molecule is most curved near the poles while it is flattened about its equator.
Because of the curvature, carbon atoms 1 and 9 an the most pyramidalizcd. Binding of
ofganomtallic reagents to fullennes results in some degree of local distortion. This
distortion arises from the added pyramidalization of the carbon atoms that arc bound
248
77).
by the added group. For C70, the most curved, and consequently most pyramidializcd,
carbon atoms am thc most thamodynamically reactive atoms in the cluster.
Multiple addition of Vaska-type complexes to C70 has also been explored. If
a d d i t i d reactivity is confmcd to the 1.9 bonds at the opposite pole of C70 then thne
double addition products can result. The possible sites of reactivity arc shown in Figure
27.where site A rcprtscnts the position that places the two added groups closest together,
site C is the site &a&positions the two p u p s funhest apart, and site B places them at an
intenaediatedistance. With the more reactive complex, Ir(CO)Cl(PMe2Ph)2, crystalline
forms of both single and double addition products have been obtained.81 The reaction is
controlled by the stoichionwry in the addition reaction. The structure of the singleaddition
product rcstmblcs that of the triphenylphosphine analog, and again, addition to a 19 bond
occurs 88 secn in Figure 28. The reaction of C70 with a 6- to 12-fold excess of
Ir(CO)Cl(PMe2Ph)2 produces a remarkably homogeneous crystalline material, (q2-
C7o)(Ir(cO)Cl~M~~~)~~3cgH6.~1 The structure of the complex is shown in Figure
28. The product has a structure that cornsponds to addition to site B of Figure 27. That is
the site that places the two added groups at an intermediate distance apart. In this double
addition product, all of the four phenyl rings hug the C70 unit and arc involved in
intratnolccuit~~ z-zcontact.
o a
o b
@ C
o e
o d
@ C
o b
a a
B
Figure 27. A diagram that shows thc pmbable sita for ddition of a sccond iridium complex to C70 if
first lddirion impedes sddition tothcsamcplc ofthccclrbon clusta(fran ref- 81).
0
c37
c5
251
5.2 Osmyhtion
Treatmat of C70 with osmium tetroxrde in pyridine produces two isomeric single
addition ptOducts.*f These have been separated by chromatography. Structural analysis
by 1% NMR spacaoscopy has shown that the two products involve addition to the 1.9 and
7,s bonds (pigwe 25) in the cluster. Drawings of the smctures of these two isomers am
shown in Figure 29. The ratio of amounts of the 19 addition product to the 7.8 addition
product is 2.1:l. Addition to the 1.9 bond, which is the more prevalent, follows the
pattern sccn in the addition of Vaska-type complexes. The pattern of kinetic addition seen
for the mylation appears to be mntrolled by two factors; the reactivity as expressed in
the 1;bondordcr, and the degree of local curvature within the fullerenene. The 1,9and 7,8
bonds have the highest x bond order, and consequently should be the most reactive .
However, on this criterion alone, the 7,s bond should be the most reactive, yet the 1,9
isomor is man prevalent. The greater reactivity of the 1.9 site has been attributed to the
greater degree of curvature at that site and the degree of pyramidalization of the carbon
atoms,w This a n d has also been noted for the thermodynamically controlled addition of
vaska-typecomplexes to c7o.n
0 PY
Further addition of osmium tetroxide to these two separate single addition products,
results in the formation ofmixtures of double addition products. From the reaction of the
1.9 isomer. six chromatographically separated double-addition products have been found,
while with the 7,8 isomer seven double-addition products were obtained. Four of the
252
products in the two sets apparently had similar chromatographic behavior. The formation
of these distinct sets of products is a further indication that the osmylation is kinetically
ControlIcd
6 . Addition to C76, Osmylation
Osmylation of C76 in the presence of the chiral Sharpless cinchona alkaloid l i w d s
has been used for the kinetic resolution of this c h i d fullmne into its enantiomas.85
Figure 30 shows a view of C76 which contains 30 different carbon-carbon bonds with
fifteen of these at 6:6 ring fusions.851~~ If osmylation occurs at the sites of highest
cwaturc or pyramidalization (as it does in C70) then the two bonds designated 1 and 5 in
Figure 30 are the likely sites for reaction. The resolution process has involved addition of
one equivalent of osmium &@oxideto raccmic C76 in the presence of an excess of the chiral
ligands. Unreactcd c76 was chromatographically separated fromthe complexed fullttene.
The complexcd fuilerene was raduccd with tin(n)chloride in pyridine to l i b = the c76
enantiomcr. The isolated and purified enantiomers were characterized by their circular
dichroism spectla which show a rich array of features in the 300 to 800 nm @on.=
7 . Addition to c g 4
In the conventional contact arc process. C a is one of the wort abundant higher
fullaenes,76but its structural charactaisticsare mon complex than the othcr fullcrcnes that
have been tnated with organomctallic reagents. The 24 isolated-pentagon smctuces87 that
can be drawn for it have &en shown to fall into two disjoint families88 which c ~ l lbe
intcrconvmed through the pyracylene of Stone-Wales transformation.@' Within the p u p
of 24 isolated pentagon isomers the arc four D2 and two DZd isomers as well as isomefi
with different symmetry. Calculations indicate that the specific & (22) and (23)
isomers that am shown in Figure 31 an lowest in energy.% 13C NMR studies of Cgq have
concluded that the 32 line pattern can be explained by the presence of a 2: 1 mixture of the
D2 (22) and b (23) is0mers>19~but no effective chromatographic separation of these
isomers has been found.
Treatment of a saturated benzene solution of C84 with an excess of
Ir(CO)CI(PPh3)2produced black Crystals Of ( ~ 2 - c ~ ) ~ r ( c o ) ~ ~ ( P P h ~ ) The ~04c~6.93
structtln of the complex as determined by a single crystal X-ray diffraction study is shown
in Figure 32. While the complex itself has no crystallographically imposed symmetry, the
geometry of the Cw moiety corresponds to that of the (23) isomer. The distance along
the axis that bisects the C(32)-C(53) and C(42)-C(43)bonds is 8.61 A, while the distance
amom the two axes that an perpendicular to this is 8.34 A. he iridium ion is coordinated
to the C(32)-C(53) bond, which is only one of the 19 different types of C-C bonds in Csq.
HUckel calculationsindicate that this is the bond in Cw that has the highest x-bond order,
and thenfore it should be the most reactive.77 As a consequence of coordination, the
C(32)-C(53) bond length (1.455 (6) A) is considerably longer than that of its counterpart,
the C(42>c(43) bond (1.332 (1 1) A) at the oppositepole of the fulleme.
carefulexamination of the fullerene portion of the structurereveals the presence of
a degrec of disorder. During rcfmement, difference maps revealed electron density in the
hexagons that were adjacent to three bonds: C(17)-C(18), C(42)-C(43). and C(67)-C(68).
Figm 33 shows the location of these additional carbon atoms. In each case the pattern is a
supexposition of that given by the Stone-Wales transformation.89 No other orientationof
the (23) isomer of Csq would produce such a set of added peaks, but the presence of
small amounts of other isomers could produce these features. However, an unambiguous
identification of which other isomer (or isomers) was present was not possible.
Nevertheless, adduct formation and crystallization has produced a sample that consists
pdominantly of the (23) isomer. The selective crystallizationof the Dzd (23) isomer,
which is suspected to be less abundant than the & (22) isomer, may result from a stronger
tendency of that isomer to form adducu. Hiickel calculations show that the Du (23)
isomer has the most localized x-bonding of the fullerenes that have been isolated, and it has
been suggested that it will be the most reactive towad addition reactions.7
Since three different fullerenes, C a , C70, and C84. have all been structurally
charactaized with the samc organometallic p u p , Ir(CO)Q(PPhjh. aff'iied to the exterior,
it is revealing to compare the three. Figure 34 presents a view of this to scale so that the
d i f f ~ n c c in
s sizes and shapes of the thre fullerenes arc apparent.
254
c s the
Figure 31. Ideal s t ~ ~ h ufor (23) and (22) isomus of c84. (from referem 93). The
n u m h in pamthesi refer to the tabulation of isomers in nfaence 87.
C
3
.
2c
QJ
c
m
3
.L
%
<
P
- . ic. . I . . . I
featum at 380,500and 680 nm are characteristic of the endohedral complex since they do
not appear in the spectrum of C84 itself. The external shape of sCz@(384 has been
examined by scanning-tunneling-microscopy.lw The images show a roughly spherical
shape of the molecules with no protrusions. Consequently, it was concluded that the
scandium atoms were indeed encapsulated within the cluster. However, some variation in
external shape is evident in the images, and this may be due to intrinsic asymmetry of the
cluster and or the presence of isomeric species.lw
By working under anaerobic conditions, it has been found that a number of newly
detected and air-sensitive metallo-fullerenescan be extracted.110 Several new lanthano-
fullcmncr have been detected by epr spectroscopy and mass spectroscopy in this fashion.
Lanthrnumcarbide has been found to give improved yields of these lanthano-fullerenes. 111
hother article reports that contact arc vaporization of graphite in an atmosphere of
Fe(C0)s yields an extractable material that may contain The material was
subjected to chromatography but not efficiently separated from other fullerenes. It has been
examined by M6ssbauer and Fe-K EXAFS measurements.
The isolation and purification of these endohedral complexes is an exciting and
wclcom advance in this field.1139114 It may be anticipated that this work will lead to more
detailed information on the structure and physical properties of these remarkable molecules.
Acknowledgments
1thank the U. S.National Science Foundation for support of fullerene research at
Davis, Marilyn Olmstead and Bruce No11 for their crystallographic work, Joong Lee and
Bmce Noll for help with the graphics, h a Ginwalla, Dave Costa and Joong Lee for their
experimentalcontributions, Joe Calabrese for providing some crystallographiccoordinates,
and Eileen Rivera for help in preparing this document.
258
References
Fullerene-contaioing Polymers
Roger Taylor
From the time that they were discovered, the possibility of using fullerenes in the
formation of polymers has been very much in the minds of chemists and materials
scientists. Three main possibilities arise: a) The polymer may consist of linked fullerenes
(either directly or by means of a small 'spacer') giving polymers of the 'pearl necklace'
type); b) the fullerenes may be attached regularly to a polymeric backbone chain (giving
a pendant chain effect); c) the polymer may have the fullerene as a relatively small
percentage of the overall composition, the hllerene molecules being located at
structurally significant points. The latter group includes the copolymers.
Giver the current high cost of fullerenes, only polymers of the latter category
have any prospect of being utilised at the present time, and good progress has been made
in creating polymers showing promise of having special applications.
1. 'Puui-Neckface' Polymers
1. I Directly-linked Fullerenes. The simplest pattern that can be envisaged here is that
shown in Figures 1 and 2. None of the former type are yet known, but the latter can be
produced by irradiation of the fullerene in the absence of oxygen (which quenches the
first excited triplet state of [60]fullerene and hence reaction) by either W or visible light,
resulting in a (2 + 2) cycloaddition of up to twelve [6O]fullerene The
product is no longer soluble in toluene, but can be dissolved in boiling isodurene. Given
that the number of double bonds in [6O]&llerene is thirty, numerous conformations of the
product are possible. However, twelve of these are sterically precluded, and the
263
264
polymerisation. 899 For example, the peak corresponding to 10c60 was 500 amu
deficient, correspondingto the loss of 42 carbon atoms. Possible structures for the dimer
have been considered, and their energies calculated. These showed that the dispirane (1)
could be the structure for C118 and it is relevant therefore that a related spirane
stmcture (2) has also been proposed (based on chemical reasoning) for the structure of
CI19 produced fiom ~600.10
(1) (2)
1.2 1.rectIy-linkd Fullerenes. Figure 3 shows the next most simple polymeric
fillerem stmcture that can be envisaged, i.e. involving a spacer group.
t. n
Although there is no evidence yet for the presence of the hydrogen shown in such
polymers, they (or some other group) are necessary if an exceptional amount of bond re-
organidon in the cage (and the unfavourable placement of double bonds in pentagonal
rings) is to be avoided, as would be the case if R groups alone are present. However, the
latter mmgement has been assumed to exist in the polymer C60Pdn formed from
[6O]hIlerene and the complex Pd2(dibenzylideneacetone)3CHC13 (which undergoes
ligand diaplacement.If Large values of n were associated with the use of large
stoicheiemetricquantities of the complex, but n was never less than one if [6O]fbllerene
was in excess, consistent with a chain having one palladium per fbllerene cage. On
heating the polymer, some [60]Mlerene is released, and the value of n increases to ca. 3,
consistent with the formation of a lattice polymer. For n values > ca. 3, the polymer
266
1.3 Copijmers. In this sub-division of the previous group, the fbllerenes appear within a
polymex chain, but the inter-lllerene length can be considerable. The fullerene can be
incorporated either as the other component of the polymer is formed fiom monomer, or
attached subsequently to a preformed polymer chain; both techniques have been used.
1.3.1 Atlachment of a Fullerene to a Preformed PoI'er Chain. A polymer with indirect
links between the fullcrenes was obtained by reacting non cross-linked polystyrene with
fbllerenes in the presence of aluminium trichloride, to give Lewis acid-catalysed
akylaticm of the fullerenes and a highly cross-linked product.15 An alternative
procedure hss made use of the fact that fbllerenes are highly reactive towards anions and
nucleophilca. Polyethylene films, functionalized with diphenylmethyl groups, have acidic
hydrogens present as a result of these groups. Deprotonation may be therefore affected
with e.g. b u t y l - l i t h i u m - ~ ~ ~ , ~ - t e t r a m e t h y I ~ h y l e n etod i ~give
e an anionic
polyethylene surface which then attacks [6O]lllerene to give, following quenching with
methanol, the fullerene incorporated polymer; properties were not reported.16
In order to try to circumvent the all-important solubility problem, polymers have
been made in which [6O]lllerene is added, through cycloaddition, to azido-substituted
polystyrmss (44 b, c). After N2 loss, these polystyrenes react with [6O]lllerene to give
the corresponding Illerene-containing polymers (5% b, c). Mainly mono(cyc1o)addition
occurs and so there is relatively little cross-linking. In these products, the respective
amount of [6O]lllerene incorporated is 5.5,21, and 29 wt.-%, and the products are very
soluble in organic solvents. The molecular weights range from 27,000 (polydispersity
2.04) to 38,500 (polydispersity 3.12), and the respective glass transition temperatures are
112, 142, and 160 "C compared to 97 "C for azidopoiystyrene.17Note that in these
polymers, nitrogen inserts into the bond common to a 5- and a 6-membered ring.
268
(4), a) x = 99, y = 1
b) x = 94, y = 6
c ) x = 8 9 , y = 11
Me-qH-CH2-O-[CH-CH2-0ln-CH2-$H-Me
NH2 R NH2
(6, R = H, Me, n variable)
for [60]hUerene) has been used as shown in Scheme 3.19 The polymers contain ca.
200 mg of fillerene per gram of polymer, and (7a) is soluble in toluene and carbon
disulphide.
I
I
This technique has also been used in the reaction between[60]hllerene and
amine-fhctionalised ethylene-propylene terpolymer (Scheme 4).20 Reaction was
brought about by stirring the reagents together for 1 week at room temperature. The
polymer was precipitated with acetone, redissolved in THF or hexane to give a reddish
product, soluble (except for cu. 5% attributed to cross-linking) in xylene.
2. Dendrimers
The technique used to prepare the polymers (5) shown in Scheme 2, has also
been used to prepare dendritic hllerenes or dendrimers. The polymer shown in Figure 7
is, like the polymers (S), also very soluble in organic solvents, has a glass transition
temperature of 325 K (again higher than that, 3 12 K for the initial azide), and is formed
with only 5% of diaddition to the hllereneF2 as might be expected in view of the large
steric hindrance in the addend.
3. Starfolymers
Use here has also been made of the fact that fi~llerenesare extremely reactive
towards anions.By reacting [60]&llerene with a living poiystyrene anion, polymers with
the formula [60]fillerene(p0Iy~tyrene)~, where x = 1 - 10, have been obtained (Scheme
51.24 There was a trend to formation of higher molecular mass species as the
CH3-CHz-CH-Li + styrene
I
Scheme 6 Formation of a star polymer by reaction of fulbrenols with urthane polyether prcpolymer
4. Electroactive Polymers
Cyclic voltammetry of 6 1,61-bis(trimethylsilylbutadiynyl)-1,2,-dihydro-1,2-
methano[60]fillerene(8) showed a single well-defined one-electron reduction at 1.OO v.
During repeated potential cycling (0.1 vfs), the voltammetric peak current increased with
273
the number of scans, due to the formation of an immobilised electroactive coating on the
electrode, believed to be an air-stable polymer. The fact that the film continued to build
up even after it had covered the electrode suggested that it is electrically conducting.,
and can be used as an electrode material.26
Referenceu
7440.
8. C.Yeretzian, K Hansen, F. Diederich, and R. L. Whetten, Nature, 359 (1992) 44.
9. M. At4 N, Takahashi, and K. Nojima, J. Phys. Chem.,98 (1994) 9960.
10. R. Taylor, J. Chem. Soc., Chem. Commun., (1994) 1629.
11. H. Nagashima, Y. Saito, M. Kato, T. Kawanishi, and K. Itoh, J. Chem. SOC.,Chem.
Commun.,(1992) 377.
12. M. F. Meidine, unpublished work.
13. T. Suzuki, Q. Li, K. C. Khemani, and F. Wudl, J. Am. Chem. Soc. 114 (1992)
7300.
14. S.Shi, K. C. Khemani, Q. LI, and F. Wudl,J. Am, Chem. SOC.,114 (1992) 10656.
15. G. A. Olah, I. Bucsi, C. Lambert, R. Aniszfeld, N. J. Trivedi, D. K. Senshanna, and
G. K. S. Prakash,J. Am. Chem. Soc, 113(1991)9387.
16. D. E. Bergbreiter and H. N. Gray, J. Chem. Soc., Chem. Commun., (1993) 645.
17. C. J. Hawker, personal communication.
18. N. Manalova, I Rashkov, F. Beguin and H.van Damme, J. Chem. Sot., Chem.
Commun., (1993) 1725.
19. K. E. Geckelerand A. Hirsch,J. Am. Chem. Soc.,115 (1993)3850.
20. A. 0.Patil., g. W.Schriver,B. Carstensen, and R. D. Lundberg, PoZe'r Bull., 30
(1993) 187.
21. D. A. Loy and R. Assink, J. Am. Chem. Soc.,114 (1992) 3977.
22. C. J. Hawker, K. L. Wooley, and J. M. J. Frechet, J; Chem. Soc.,Chem. Commun.,
(1994) 925.
23. K. L. Wooley, C. J. Hawker, J. M. J. Frechet, F. Wudl, G. Srdanov, S. Shi, and M.
Kao, J. Am. Chem. Soc., 115 (1993) 9836.
24. E. T. Samulski, J. M. DeSimone, M. 0.Hunt, Y. 2.Menceloglu, R.C. Jam&, G.
A. York, K. B. Labat, and H. Wang, Chem. Muter., 4 (1992) 1153.
25. L. Y.Chiang, L. Y.Wang, S. Tseng, J. Wu, and K. Hsieh, J. Chem. Soc.,Chem.
Commun.,(1994) 2675.
26. H. L. Anderson, C. Boudon, F. Diederich, J. Gisselbrecht, M. Gross, and P. Seiler,
Angew. Chem. Intl. W n .Engi., 33 (1994) 1628.