Review

pubs.acs.org/Organometallics

Fifty Years of Ziegler−Natta Polymerization: From Serendipity

to Science. A Personal Account†
John J. Eisch*

■
Department of Chemistry, The State University of New York at Binghamton, Binghamton, New York 13902-6000, United States
PROLOGUE of not only natural products but also the large-scale production of
At the end of some 55 years in university teaching and research, I organic compounds of broad pharmaceutical importance. To the
find myself considered as an organic researcher well-known in inorganic or physical chemist, on the other hand, the structural and
the discipline of organometallic chemistry. With their air- and physical properties of organometallics challenged the boundaries of
moisture-sensitive carbon−metal bonds, organometallics are existing valence theory and promised deeper insights into the
clearly the antithesis of the naturally occurring organic com- complex nature of chemical bonding. Although these two separate
pounds and their simpler derivatives, which are composed of viewpoints, the value in fundamental organic synthesis versus the
carbon, hydrogen, oxygen, nitrogen, sulfur, and phosphorus, and complex structure of organometallic compounds, enjoyed broad
for over a century have been the focus of mainstream organic importance in academic chemistry and the production of specialty
chemistry. Prominence in organometallics was not at all my goal organics, neither of these efforts had generated any great interest in
when I began the study of chemistry at Marquette University. industrial chemical processes prior to 1950. This compartmentalized
Although I was already committed to organic chemistry from academic pursuit of organometallics into utility in synthesis or into
work in my home lab and high school chemistry, my attraction relevance to chemical structure was to be swept away with the
narrowed rapidly to the field of natural products and thereafter to completely unexpected discoveries in the pentad of 1950 to 1954,
carbohydrates.1 As a result I carried out research on the sugars embracing as structural surprises the syntheses of ferrocene and
found as hydrolysis products of okra pods and prepared a honors other cyclopentadienyl and arene−transition-metal complexes and
senior thesis2 under the direction of Professor Clifford the discovery of facile, stereoselective olefin oligomerizations
Haymaker3 (Figure 1) of the Chemistry Department and Dr. or polymerizations by transition-metal salt combinations with
Kenneth Brown, a young biochemist in the Marquette School
of Medicine.4 On the strength of this thesis and my overall
academic record, I was awarded a competitive, four-year
scholarship for doctoral study in paper chemistry at the Institute
of Paper Chemistry, then in Appleton, Wisconsin. I was assured
that such study could lead to a position as a research chemist in a
paper mill. I thus undertook the first semester of study at
Lawrence College, affiliated with the IPC, with great enthusiasm.
As the semester wore on, however, I enjoyed the organic
chemistry greatly5 but found the parallel classes in engineering
and physics rather routine and unexciting. Discussion with my
classmates gradually made clear to me that upon graduation I
would most likely end up managing a paper mill. That outcome
was not what I wanted, and so again with the guidance of
Professor Haymaker, I resigned my scholarship after one semester
and obtained a research fellowship at Iowa State University with
Professor Henry Gilman. In this way began my journey from
conventional natural products chemistry to “unnatural” organo-
metallic compounds.

I. INTRODUCTION
A. Organometallic Chemistry Prior to 1950. The status of
organometallic chemistry, right after World War II, was that of an
esoteric, marginal academic discipline bordering on both organic
and inorganic chemistry and concerned with the structure and
properties of ionic or covalently bonded organic derivatives
containing a direct carbon−metal bond. Already a century-old
discipline since Frankland’s pioneering research on zinc alkyls in
1849,6 organometallics were regarded from two distinct points of
view. The organic chemist valued the C−C bond-making ability
of Grignard and organolithium reagents as presenting unique and
selective methods for the complex and stereoselective synthesis
Figure 1. Clifford R. Haymaker (1907−1981). Born sightless in
Milwaukee, Wisconsin, he made his way with sighted tutors through
grade school, high school, and Marquette University with the highest
honors and finally obtained the Ph.D. degree from Marquette University
in 1938 with the dissertation “The Chemistry of Atomic Nuclei”. He
offered lectures at Marquette on all levels of organic chemistry with the
aid of student scribes from 1938 to 1968. He retired with the rank of
professor and the warm regard of his many grateful students. Biography:
Eisch, J. J.; Haworth, D. T. J. Chem. Educ. 2003, 80, 275.
Received: April 26, 2012
Published: July 2, 2012

© 2012 American Chemical Society 4917 dx.doi.org/10.1021/om300349x | Organometallics 2012, 31, 4917−4932
Organometallics Review

main-group alkyls as an unexpected boon to synthetic organic interest. As will be brought out later, I had developed a strong
chemists. This list of some pathfinders in this period, chiefly Reppe, interest in the German language and literature since my youth and
Roelen, Pauson, E. O. Fischer, Wilkinson, Ziegler, and Natta, from my family heritage. However, the more important and
conjure up the heroes in these revolutionary developments.7a,b immediate connection was the long-standing relationship between
B. The Gilman−Ziegler Connection during My Doctoral Henry Gilman and Karl Ziegler. Gilman and Ziegler had been
Studies at Iowa State University. When I began doctoral
studies at Iowa State University in January of 1953, I was follow-
ing the trusted counsel of my major advisor at Marquette University,
Professor Clifford Haymaker, who had sent a number of Marquette
seniors to study with Professor Henry Gilman.8 Gilman was already
world famous both for his voluminous publications on main-group
organometallics and heterocyclic compounds and as a legendary
taskmaster in his training of graduate students (Figure 2). I was
initially more interested in heterocycles than, to me then, the peri-
pheral field of main-group organometallics, and so Professor Gilman
and I agreed upon a doctoral topic combining both themes. In
early 1956, accordingly I presented a doctoral dissertation entitled,
“Comparison of Phenanthridine with Other Aza-Aromatic
Heterocycles”,9 which concerned the use of Hückel molecular
orbital theory to rationalize the site and relative reactivity displayed by
pyridine and bi- and tricyclic pyridines toward electrophilic,
nucleophilic, and radical reagents. Naturally, among the nucleophiles
that I evaluated were both Grignard and organolithium compounds.
The further relevant connections that completed my total
immersion in organometallics as my career field were of two very
different types: one a scientific relationship and the other a cultural

Figure 2. Henry Gilman (1893−1986). After he received a Ph.D. degree

at Harvard, he spent his entire academic career at Iowa State, where his
graduate students and he published over 1000 papers. About half of
these publications were made after 1947, as retinal detachments and
eventually glaucoma rendered him sightless. He was, arguably,
internationally the most towering figure in organometallic chemistry.
Biography and appreciation: Eisch, J. J. J. Organomet. Chem. 1988, 338,
281. Eisch, J. J. Organometallics 2002, 21, 5439.

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Organometallics
Figure 3. Karl Ziegler (1898−1973). After he received a Ph.D. degree from
Marburg at age 21 (!), he held professorships at Frankfurt (Main), Heidelberg,
and Halle (1925−1943). Already world famous in 1936 for his ingenious
research on the synthesis of stable free radicals and large carbon rings, he was
guest professor at the University of Chicago. In 1943 he became director of the
Kaiser-Wilhelm-Institut für Kohlenforschung (after 1949, Max-Planck-Institut),
where his research on olefin polymerization earned him, jointly with Natta, the
Nobel Prize in Chemistry in 1963. He retired from the directorship in 1969,
and his chief research associate, Guenther Wilke, was his successor. He passed
away in 1973, upon returning from viewing an eclipse of the sun, astronomy
being his keen avocation. Biography and appreciation: Wilke, G. Liebigs Ann.
Chem. 1975, 805−833. Eisch, J. J. J. Chem. Educ. 1983, 60, 1009−1014.
friendly rivals in the field of organolithium compounds since their
independent discoveries of organolithium reagents beginning in the
early 1930s10 extending into the 1940s.11 Although their contacts
were interrupted during the war, communication recommenced
after 1945. During my graduate studies Gilman provided me with
reprints of Ziegler’s renewed and interesting research with ethylene
and organolithium reagents in the postwar period12 and most
impressive reports of his completely original studies with α-olefins
and aluminum alkyls.13
C. Prospect of a Postdoctoral Appointment in
Germany. As my research drew to a close, Dr. Roger Gillette,14
a European scientist with Union Carbide, invited me to Chicago for
an interview on a postdoctoral associateship that Carbide wished to
establish in the research laboratory headed by Karl Ziegler at the
Max-Planck-Institut für Kohlenforschung in Mulheim, in the Ruhr
region of Germany (Figure 3).15
I frankly was doubtful if I wanted more exposure to organo-
metallics and whether I wanted to work in industry, a likely
outcome of such an appointment. However, two factors favored
my acceptance of any offer made. The mechanisms involved in
Ziegler olefin polymerization were completely unknown then
and thus seemed to offered me a great scientific challenge for a
4919
Review
unique study of reaction mechanisms, a field that had seized my
interest while at Iowa State, under the influence of two younger
professors, George Hammond and Charles DePuy.16
Furthermore, while in Gilman’s group, I was extensively exposed
to Gilman’s empirical studies on the rankings of organometallic re-
activity.17 Although these rankings were then without any clear mole-
cular explanation, they served to stimulate curiosity as to mechanism.
In such rankings of the reactivity of RM types toward carbonyl
substrates, the RLi reagents showed a greater reactivity than RMgBr
types and the R3Al type displayed a much reduced reactivity com-
pared with either. Yet Ziegler now found that R3Al reagents showed a
much greater reactivity than either RLi and RMgBr reagents toward
olefins both in additions and in transition-metal-catalyzed polymer-
izations. (For further discussion of the diminishing effect of coordina-
ting solvents, such as ethers and tertiary amines, on the reactivity of
aluminum alkyls, cf. section III.A.)
As mentioned above, a second factor enhancing my interest in
such an appointment was my German heritage. My grandfather
on my father’s side came from Bavaria through a long line of glass
workers reaching back to Bohemia before the 1600s. My
grandfather, Josef Eisch, immigrated to the United States in 1880
with his (then) family of six. Three further children were born in
the United States, of which my father, Frank Joseph, was the
youngest.18 Although a glassblower by trade, my grandfather had to
abandon that work, as mechanical bottle-making machines took
over his function in the X-ray tube and even glass bottle industries.
My father eventually moved to a German community in
Milwaukee,19 where with his brother William he established an
automobile, battery, and tire-repair shop. Remaining in Bavaria were
my grandfather’s brother, whose offspring lived in Frauenau,
Bavaria, and founded a glass works, the Glashütte Eisch, in 1949
after working for centuries for local gentry. After World War II my
much older first cousin in Milwaukee, coincidentally named Joseph
Ziegler (!) reestablished contact with the Bavarian Eisches.
Many of my friends were also of German background. In fact,
my best friend in high school, Robert Heinen, came from a
German-speaking family, and through him I developed an early
interest in spoken German and its literature. Finally, I studied
German for 2 years at Marquette University and to my personal
satisfaction won first prize in the Gottfried Keller competition in
German literature translation. I attribute my success in mastering
spoken and written German to my four years of studying
Classical Latin at St. John Cathedral. With its five declensions of
nouns and four conjugations of verbs, Latin was an excellent
preparation for the intricacies of German.
Thus, in my meeting with Dr. Gillette and his inquiry about my
knowledge of German, he became most interested in my suitability
for the Ziegler Fellowship upon learning about my keen interest in
German and promptly offered me a 2 year postdoctoral appoint-
ment to start in April of 1956. After consulting with my wife, Joan, I
readily accepted the offer. However, it was the courage of Joan that
really was decisive: at the time she had just borne our first child,
Margaret, who was then 11 months old and was expecting our
second in June 1956. She had graduated in 1952, also from
Marquette, with the Bachelor of Science degree in nursing and thus
was better prepared than most American women for the surprises
and apparent vagaries of German medical practice.20,21
II. RESEARCH IN THE STRANGE REALM OF
RECUPERATING EUROPE
A. Passage to Germany. We departed from Milwaukee in
April 1956 after I received my doctorate degree that March. After a
short stopover in New York City to visit administrators of Union
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Organometallics
Carbide and the German Consulate for the required visas, we
undertook, with baby Margy in our laps, the long, tedious, propeller-
driven flight to Brussels, where Union Carbide had just established
the European Research Associates Laboratory in an old chateau in
the Brussels suburb of Uclle. This was to be a fundamental corporate
research facility meant to attract talented European scientists who
could not be lured away from their European roots. After several
days of getting acquainted with ERA scientists with my adequate
English and German but minimal French, my family and I took the
evening train to Cologne, where we were met by my principal
mentor while at the Max-Planck-Institut für Kohlenforschung, Dr.
Guenther Wilke, one of Karl Ziegler’s chief co-workers (Figure 4).
Switching to conversational German proved to be difficult initially
but I had resolved against retrogressing into English. (No German
was to learn English from me!) During the first 2 weeks in Mülheim,
a devastated industrial city in the Ruhr near Essen and only barely
restored, we resided in the only hotel left standing from the war, as
Dr. Wilke guided us in finding a furnished apartment, one above a
small candy factory, and a serviceable auto, an Opel.22
B. Ziegler’s Proposal of My Research Project on
Gallium and Indium Alkyls. I began research under Wilke’s
direct guidance on a problem presented to me in my first discussion
with Professor Ziegler. With all of the novel and unusual chemical
reactions the Ziegler group had discovered involving olefins and
Figure 4. Guenther Wilke. Born in Heidelberg in 1925, at whose
christening Karl Ziegler served as godfather. After World War II he
obtained the Ph.D. at Heidelberg and joined the MPI as research
associate. His research focused on the influence of transition-metal
catalysts in novel Ziegler organoaluminum-promoted oligomerization
and polymerization of olefins and diolefins and became a dominant
figure in transition-metal-catalyzed hydrocarbon transformations. He
was the principal mentor of John Eisch’s research at the MPI during the
1956−1957 residence. He became the director of the MPI beginning in
1969 and continued in this office until his own retirement in 1993.
4920
Review
either aluminum alkyls or combinations of aluminum alkyls with
transition-metal salts, the question naturally arose: how would the
alkyls of gallium and of indium (metals congeneric with aluminum
in group 13) behave toward unsaturated hydrocarbons? In addition,
Ziegler noted how relatively expensive gallium metal was, in
comparison to aluminum (in 1956, about 10 times more costly). He
reasoned that a knowledge of the difference in physical properties
among these three types of alkyls might offer a way to separate small
amounts of the expensive gallium from the much cheaper
aluminum. His co-workers told me later that his interest in isolating
gallium from bulk aluminum was typical of the economic motivation
underlying all of Ziegler’s fundamental studies.
In parting, Ziegler presented me with a 20 gram lump of gallium
(which softens in the hand) and then admonished me to be careful,
both because of the metal’s expense and because of the pyrophoric
organometallics that I would be working with. Although I began my
initial work in Wilke’s personal lab in the main building constructed
in 1912 (Figure 5), a long, one-floor building known as die Baracke
(hut, in German) to house Wilke’s group was complete soon after
my arrival (Figure 6).
Figure 5. Façade of the Max-Planck-Institut für Kohlenforschung;
founded in 1912 as a Kaiser-Wilhelm Institut. The length of the original
building is about three times the width of this façade (cf. Figure 10). A
lecture hall was added behind the main building in 1929.
To the left in Figure 6 and shown in a different viewing was the new
Versuchsanlage (pilot plant), where large-scale olefin−aluminum alkyl
reactions were conducted (Figure 7) Although externally of wood
framework, internally die Baracke was all ceramic, concrete, and steel
to minimize the fire hazard (Figure 8). As my first demonstration of
the dangers I would encounter, one of the group leaders, Hans Breil,
equipped with a face shield and leather gauntlets, loaded a 10 mL pipet
having a plunger with triethylaluminum under argon and squirted the
contents down the lab’s central aisle. The vivid flame-thrower effect of
the burning alkyl made an indelible impression on me, and I needed no
further reminder to be aware, careful, and frightened.
The average German graduate student then might have been
less acquainted with modern electronic theory than his American
counterpart would have been in planning actual laboratory
experiments, but the German’s training in research execution was
far superior to any skill that I and my American contemporaries
would have acquired during doctoral study. Because of both the
moisture and oxygen sensitivity of main-group organometallics,
as well as the poor quality of research chemicals and solvents then
available in Germany, chemists at the MPI had to undertake
lengthy purification procedures to secure reagents and solvents
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Organometallics
Figure 6. The façade of the MPI-Baracke, the temporary laboratory for
the Wilke research group during 1956 to 1981, is in the foreground. The
length of this one-story building was four times the width of the façade.
At the same time, the pilot plant (Versuchsanlage) on the left was also
constructed. The new 10 story research center in the left background
(Laborhochhaus) was opened in 1967.
Figure 7. The pilot plant ((Versuchsanlage) where large-scale reactions
of ethylene with aluminum alkyls were conducted under pressure.
Occasionally when such a reaction went out of control, a spectacular
fiery explosion would result.
Figure 8. The interior of the Baracke, where all lab benches, shelves, and
apparatus supports were made of cement, brick, ceramic, glass, and/or
metal, not combustible in case of fire. John Eisch’s research bay was the
third bench toward the rear on the right side: in an emergency,
comfortably close to an exit.
4921
Review
suitable for organometallic research. Furthermore, the preferred
inert atmosphere for such reactions, the denser-than-air argon,
had to be thoroughly deoxygenated and freed of any proton
sources, ranging from water through alcohols and extending to
terminal acetylenes. Finally, the root cause of many of Ziegler’s
astonishing discoveries stemmed from the catalytic action of
transition-metal salts, such as nickel, zirconium, and titanium, on
main group alkyls, so that after the astonishing and unexpected
effects of such salts on aluminum alkyls were revealed, excluding
any trace of such salts from the aluminum used or from the metal
autoclave reactors became a crucial factor. My fellow co-workers
in Wilke’s group and Guenther Wilke himself freely offered
indispensable advice to this neophyte in undertaking this
hazardous, demanding, but most exciting research.
III. MÜ LHEIM AS THE WORLDWIDE MECCA FOR THE
CHEMICAL INDUSTRY
A. Advances in Main-Group Organometallics after
1950. After 1945 research on the prominent main-group-metal
alkyls resumed along the same lines, where the applications of
Grignard and organolithium reagents to organic synthesis were
vigorously explored, principally in the research groups of Henry
Gilman and Morris Kharasch in the United States and by Georg
Wittig and Karl Ziegler in Germany. Most of the synthesis pro-
cedures involved diethyl ether as the preferred solvent, although the
introduction of tetrahydrofuran (THF) as an adjuvant medium by
Henri Normant in 19547b was immediately accepted as a great
improvement as to reaction rate or yield. As a result, when Gilman
carried out studies of the comparative reactivity of phenyllithium,
phenyl Grignard reagents, and triphenylaluminum toward ketones,
such as benzophenone, the reagents showed a reactivity decrease in
the order PhLi > PhMgBr > Ph3Al. It has been subsequently shown
by our group23 that aluminum reagents in ether solution form a Lewis
complex (3), which reacts at a much slower rate than the unsolvated
monomer (1) or dimer (2) (eq 1). Because of this retarding effect of
Lewis bases on the reactivity of R3Al, their reactivity toward olefins or
acetylenes remained undetected until Ziegler’s work in the early
2R ′2 O
(R3Al) ⇌ 2R3Al ⎯⎯⎯⎯⎯→ 2R3Al·OR′2
2 1 3 (1)
1950s. (An anonymous reviewer has poetically referred to solvated
aluminum alkyls 3 with their muted reactivity as “sleeping beauties”.)
B. Ziegler’s Research with Unsolvated Main-Group
Alkyls.24 Actually in his pioneering work with Colonius, Ziegler had
first synthesized alkyllithium (5) from alkyl halides (4) and lithium
metal in alkanes or benzene, from which the resulting lithium halide
(6) cleanly precipitates (eq 2). Furthermore, the RLi reagent proved
to be much more stable in hydrocarbons than in ethers.
Gilman, Zoellner, and Selby soon found that the preparation
and subsequent reactions of lithium organyls (R = alkyl, aryl)
proceeded rapidly and more efficiently in ether in the range of
25 °C or lower (eq 3). Thus, subsequent research was conducted
in diethyl ether or tetrahydrofuran, solvents that coordinate with
aluminum or organyls and slow down addition to either carbonyl
or carbon−carbon unsaturation.
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Organometallics
When Ziegler recommenced his research with lithium alkyls in
the late 1940s, employing as his model systems ethyllithium and
n-butyllithium,12 it was natural that he would employ these
reagents in a hydrocarbon solvent, as prepared according to eq 2. The
choice of a hydrocarbon solvent for these reactions of formaldehyde
or ethylene proved to be fortuitous, since ethyl ether would
have inhibited the RLi from addition of ethylene to the carbon−
lithium bond of RLi (vide supra, eq 1) and instead the ether would
have been cleaved (eq 4). Not only did the alkyllithium added still
add slowly to formaldehyde but also under ethylene pressure added
1−15 ethylene units to the carbon−lithium bonds to give oligomeric
α-olefins after the elimination of LiH (Scheme 1). Although the
Scheme 1
oligomerization was slow and complicated by resin formation via 8,
Ziegler reasoned that such a repetitive insertion of ethylene units
into an appropriate carbon−metal bond could lead to a linear
polymerization of the hydrocarbon chain.
Reinforcing this surmise of possible formation of a linear poly-
meric alkyllithium were related observations made in the attemp-
ted purification of ethyllithium by sublimation under high vacuum.
In the immediate postwar period the necessary vacuum equipment
simply was not available. Hence, upon heating under the attainable
reduced pressure ethyllithium underwent complete decomposition
into lithium hydride and a homologous series of even-numbered
α-olefins ranging from ethylene up to 1-dodecene in sharply diminish-
ing proportions. In a neat, serendipitous explanation Ziegler
concluded that such products were explicable by the reactions in
Scheme 1, proposed for the multiple insertion of ethylene units into
the starting ethyllithium.
C. Ziegler’s Pioneering New Departure (Auf bruch, in
German) in Organometallic Chemistry. With the hope of
bypassing the preparation of ethyllithium, the addition of
ethylene under autoclave pressures to powdered lithium hydride
(mp 680 °C) was studied (eq 5) but was found to be ther-
modynamically impractical. In the search for a more covalent
metal hydride having a smaller negative lattice energy, Ziegler’s
group examined the unstable LiAlH4 (9), recently reported by
Schlesinger’s group at the University of Chicago. Indeed, four
units of ethylene added to the Al−H bonds, a process later
termed hydroalumination, to form lithium tetraethylaluminate
(10). At higher temperatures and pressures (under argon) each
of the Al−C bonds of 10 underwent multiple insertions of
ethylene units to form lithium tetraalkylaluminates (11), whose
alkyl groups consisted of even-numbered carbons statistically
distributed between C4 and about C30. Hydrolysis of 11 yielded
the corresponding mixtures of even-numbered alkanes or
4922
Review
α-olefins (eq 6), the latter formed from displacement from 10
by excess ethylene (11 → 10).
LiH LiAlH4 (9)
no reaction ←⎯⎯⎯⎯⎯⎯ 4H 2CCH 2 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ LiAl(CH 2CH3)4
Δ, pres.
(5)
Since the hydroalumination of ethylene by LiAlH4 (9) (eq 4)
and the subsequent stepwise carbalumination of 10 proved much
more rapid than the process for the corresponding uncomplexed
LiH, Ziegler and co-workers removed the LiH from 10 completely
and began the unexpectedly fertile study of the behavior of
ethylene toward the labile AlH3 and the more stable R3Al.
Although some previous studies of the reactions of aluminum aryls
with unsaturated compounds had been made by Gilman during the
1930s, the results indicated that R3Al adds to the CC group far
less readily than R2Mg or RLi, and then only efficiently when the
CC bond is conjugated with a carbonyl group. However, Ziegler
and co-workers found that Et2AlH and Et3Al add readily to ethylene
at 100 °C and further ethylenes were inserted to give higher
statistical mixtures of R3Al (11) (eq 7).
In retrospect, we now understand why the high reactivity of
organoaluminum compounds toward olefins went unnoticed by
previous workers. If such reactions are conducted in ether, as was
ordinarily done, stable ethereates, R3Al·OEt2, are formed, which
are unreactive toward olef ins or acetylenes.23 Fortunately, Ziegler
had employed the ether-free R3Al in his work.
The lengthening of the C−C chains of Et3Al to mixtures of higher
trialkylalumium mixtures of 11 (eq 7), termed the “growth” (in
German, “Aufbau”) reaction, was immediately recognized as a great
achievement in principle and in industrial practice. Such mixtures of
11 could be oxidized by dry air and then hydrolyzed to produce
higher even-numbered alcohols. Thus, a mixture of Et3Al and
ethylene as shown in Scheme 2 now permitted the oligomerization
of ethylene into a Poisson distribution of higher fatty alcohols, which
proved to be eminently suitable for preparing biodegradable
detergents. Ziegler’s research at this stage had not achieved a true
linear polymerization of ethylene to polyethylene or, via terminal
oxidation and hydrolysis, a 1-polyalkenol of high molecular weight,
but the oligomeric 1-alkanols (n = 1−30) rapidly found their place
in industry in soaps and detergents and as potential sources of fatty
alcohols, acids, and esters. Furthermore, Ziegler had established a
new and multifold synthesis of σ-bonded organometallics, namely
by hydrometalation, in which covalent metal hydrides add to olefins,
acetylenes, and dienes, as shown in eq 7 with Et2AlH. Through the
efforts of other researchers such hydroalumination was extrapolated
to other metal hydrides, such as those of boron (Köster, Brown),
magnesium (Bogdanovich), gallium (Eisch), silicon (Speier), and
tin (Neumann, van der Kerk).7b
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Organometallics
Scheme 2
D. Ziegler’s Discovery of the Diverse Effects of
Transition Metals on Organoaluminum Chemistry. In
the early 1950s “Ziegler chemistry” constituted a body of new
reactions for the preparation and transformations of aluminum
alkyls, whose molecular basis was a rational extension of the known
chemistry of main-group alkyls. However, his truly revolutionary
discoveries emerged from unexpected observations made during the
reactions of ethylene and other α-olefins with triethylaluminum.
Whether such astonishing findings should be attributed to pure
chance or serendipity, on the one hand, or to a rational and con-
sequential research plan, on the other, is problematic. Serendipity
connotes the making of fortunate but unexpected discoveries
through chance by an observer who is alert to their manifestation.
The other extreme, observations made as a direct result of a con-
sequential research plan, implies that the researcher have a premoni-
tion of what kind of reaction is being observed, on the basis of
previous experiments. In these transition-metal effects, which
variously caused olefin oligomerization, unprecedented polymer-
ization, metal hydride elimination, and hydrometalation, it is safe to
say that even an experienced researcher such as Karl Ziegler could
not have had a strong premonition whether one or more of these
reactions would be selectively catalyzed by a transition-metal salt. As
a consequence, Ziegler and co-workers would seem to have enjoyed
serendipity in these discoveries, even if they were alert to the
possibilities of unusual products arising from transition metals in the
reactions depicted in eq 7. In this sense, their serendipity was aided
by the dictum of Louis Pasteur: “Chance favors the prepared mind.”
Serendipity certainly played a central role in the next revolu-
tionary advance, but such chance undoubtedly found Karl Ziegler
with a prepared mind. As mentioned above, in 1950 Ziegler had
observed the capability of unsolvated ethyllithium to bring about
the stepwise oligomerization of ethylene (Scheme 1) and shortly
thereafter the superior ability of AlH3 or Et3Al to achieve similar
carbon chain growth (eqs 7 and 8). Certainly Ziegler was alert to
the possibility of carbon polymer chain growth. In repeating a
“growth” reaction (eq 8) in 1953, an anomalous result was
obtained: instead of ethylene being converted into a mixture of
higher aluminum alkyls (11), its dimer, 1-butene (13), was
almost the only product.
In the manner depicted in eq 8, intermediate 12 seemed to
have eliminated R2AlH more rapidly than it reacted with further
ethylene. The promoter for this unexpectedly facile elimination
was eventually found to be traces of nickel salts, which arose
accidentally during the cleaning of the metal autoclave. Since a
nickel salt could have such a dramatic influence on the course
of an ethylene−aluminum alkyl reaction, curiosity was aroused
as to the influence of other transition-metal salts. Then by an
“Edisonian” search Ziegler, Holzkamp, and Breil found that salts
of chromium, zirconium, and especially titanium did not pro-
mote the R2AlH elimination (as did nickel) but, instead,
4923
Review
Figure 9. Karl Ziegler observing the low-pressure polymerization of
ethylene into snow-white polyethylene in a 5 L preserves jar borrowed
from Mrs. Ziegler’s kitchen.
enormously accelerated the “growth” reaction (eq 7). Simply
passing ethylene, at atmospheric pressure, into a catalytic amount
of TiCl4 and Et2AlCl dissolved in a higher alkane led to the
prompt deposition of polyethylene (14) (Figure 9). The ease
with which such a “Ziegler” catalyst polymerized ethylene was
recognized as astounding; an earlier process developed by Im-
perial Chemicals Industries required temperatures up to 200 °C
and pressures up to 2000 atm, together with various radical pro-
moters. The properties of the Ziegler polyethylene were no less
remarkable: a melting point of 137 °C and an average molecular
weight of 3 000 000 (in comparison with various waxy poly-
ethylenes of about 100 000 molecular weight, which were
obtained under much more severe conditions) (eq 9).
The implications of Ziegler’s discovery of this new process
were numerous. Within Ziegler’s own institute the following
projects were inspired by these findings:25 (1) a search for
processes to prepare aluminum alkyls in an economical and
convenient way, (2) an investigation of the utility of aluminum
alkyls for preparing other organometallics in a thermal or
electrochemical way, (3) research on the use of organometallics
as a means of purifying or plating metals, (4) development of
industrial processes for preparing higher alcohols or α-olefins
from ethylene, and (5) extrapolation of Ziegler’s ethylene
oligomerization and polymerization findings to other olefins,
dienes, and acetylenes. These prospects offered such an
abundance of research opportunities that industrial laboratories
throughout the world soon launched similar studies.
Of much broader impact, both within the MPI and in the
worldwide industrial and academic chemistry community, was
the revelation of the revolutionary importance of transition-
metal catalysis in organic synthesis. Previous work by Morris
Kharasch had reported the useful carbon−carbon coupling
induced by late-transition-metal salts of iron, cobalt, and nickel
on Grignard reagents, and again Kharasch as well as Birch had
shown that small amounts of copper salts included with
stoichiometric RMgX could change the course of reaction with
α,β-unsaturated ketones from 1,2-addition to principally 1,4-
addition (eq 10).26
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Organometallics
E. Emergence of Unanticipated Transition-Metal
π-Complexes. However, what really thrust transition metals
into the chemical limelight were the astonishing syntheses of
novel transition-metal organometallics achieved contempora-
neously with Ziegler’s findings during the period of 1951−
1955. Adding to the excitement of Ziegler’s publication of his
findings in 1955 were contemporaneous announcements of the
discovery and the unusual structures of ferrocene or bis(η5-
cyclopentadienyl)iron (15) (Kealy and Pauson; Woodward) and
the nature of Hein’s compounds as charged bis(η6-arene)
chromium complexes (16), (Ernst Otto Fischer; Zeiss).7b These
astonishing structural prototypes of what came to be known as
transition-metal π-complexes or “sandwich compounds” inspired
the research groups of Geoffrey Wilkinson in Great Britain and of
Ernst Otto Fischer in Germany to undertake the synthesis of
many analogues of 15 and 16, some of which were to be the basis
of homogeneous metallocene olefin catalyst systems, such as the
titanium or zirconium derivatives of the open metallocene 17 and
the ansa-bridged metallocene 18, the latter of which could be
obtained as enantiomeric mixtures, resolvable into chiral
isomers.7b The availability of such hydrocarbon-soluble metal-
locenes was to have a great influence on Ziegler−Natta
mechanistic studies in the 1970s.
The outcome of this heightened interest in organometallics
was 2-fold: (1) the launching of a new branch of organic
coordination chemistry having mainly hydrocarbon or carbonyl
ligands bonded to a transition metal and (2) a thorough
reexamination of all accessible organometallics as to their
stoichiometric or catalytic behavior toward organic compounds.
As an immediate consequence, all aspects of “Ziegler
chemistry”, embracing novel organoaluminum and transition-
metal catalytic reactions, had by 1956 converted Ziegler’s Max
Planck Institute in Mülheim into a chemical Mecca for all
chemical and petrochemical companies throughout the world.
When I arrived in Mülheim in April 1956, I found that there was a
large group of German chemists and engineers occupying every
available square meter of the original institute of 1912 and that a
new “temporary” outdoor pilot plant (Versuchsanlage) and a new
one-story laboratory (die Baracke) for Guenther Wilke’s group
were under construction (Figures 6 and 7). Almost every week
groups of visiting industrial scientists and engineers, from the
United States, Europe, or Japan, were given a conducted tour
through our laboratories, where they could learn much about the
4924
Review
research facilities; however, we in the laboratories told them
nothing about what research was in progress. Mum was the word
until the particular firm signed a secrecy agreement or a
nonexclusive patent licensing agreement. Within the MPI the
rumor among the staff was that in this way Karl Ziegler would
become at once the most famous and the richest scientist in
Germany (Figure 10).
Figure 10. Final developed layout of the physical plant of the Max-
Planck Institut für Kohlenforschung at the end of Karl Ziegler’s
directorate in 1969 (aerial photo). In the foreground stands the 10 story
Research Center (Laborhochhaus), to the upper right lies the main
laboratory of the original MPI, and to the left behind the Research
Center is the future Max-Planck Institut für Strahlenchemie. The low
building, at the upper center behind the Research Center, is die
Laborbaracke of Guenther Wilke’s research group, where John Eisch
worked during his 1956−1957 residence.
F. Commercial Development of the Mülheim Atmos-
pheric Polyethylene Process and Persistent Legal
Controversy. Not only did Karl Ziegler and the MPI stand to
profit greatly from the patents issuing in 1955 onward on this
revolutionary polymerization process but also those industrial
firms holding nonexclusive licenses on such technology could
envision the huge value in the large-scale production of
polyethylene by this technology. This aspect of what is now
known as Ziegler−Natta polymerization and catalysts has
generated legal controversy lasting up to the 1980s. However,
the origin of the various disputes arose before I arrived at the MPI
from a secrecy agreement between the MPI and the Italian
chemical company Montecatini. This agreement gave their
consultant, Giulio Natta, Director of the Institute of Industrial
Chemistry at the Polytechnic in Milan, access to details of any
Ziegler process dealing with the reactions of olefins with
organometallic catalysts. In 1953 Natta took such information on
the Ziegler polymerization process back to Milan and began to
modify the TiCl4 used by Ziegler and eventually found that TiCl3,
a solid, with aluminum alkyls could convert propylene into
largely a stereoregular isomer of polypropylene, namely isotactic
polypropylene, as determined by X-ray analysis. Naturally Natta
and Montecatini began to obtain patents on their own, in direct
competition with Ziegler’s patents at the MPI. With now two
startling discoveries, the low-pressure polymerization of ethyl-
ene, propylene, and other α-olefins and the stereoregular variants
of isotactic, syndiotactic, and atactic of α-olefin and 1,3-alkadiene
polymers of differing properties, industrial laboratories world-
wide took up the chase for new catalysts. In addition to
Montecatini, some of the first competitors in this search were
DuPont, Standard Oil of Indiana, Phillips Petroleum, and
Hercules Powder.27 Even Karl Ziegler agreed that Giulio Natta’s
independent discovery of stereoregular polymerization was an
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Organometallics Review

important scientif ic f inding that Ziegler’s team would not have

conceived (during my stay Wilke told me of Ziegler’s open
admission of this contribution). When the Nobel Prize was
jointly awarded in 1963 to Ziegler and Natta for the scientif ic
discovery of Ziegler−Natta polymerization, there was apparent
harmony between the MPI and Natta’s group. However, the
Nobel Prize did not end but only intensified the legal dispute
over the inventorship of what Ziegler’s associates considered “the
Ziegler catalyst”. This and many other legal contentions
continued on between 1954 and 1975 concerning various
heterogeneous olefin polymerization catalysts. Fortunately, for
those interested in the myriads of patents, publications, and
litigations exemplifying this persistent legal battle, an excellent,
well-considered review of such empirical studies has been
published by an impartial industrial scientist, John Boor, Jr.27
Long after Ziegler and Natta died, in 1973 and 1979, respectively,
the legal struggle carried on between the MPI, headed by Heinz
Martin and other co-workers of Karl Ziegler, and various
industrial firms over the legal inventorship of the catalyst for this
olefin polymerization process not only for ethylene but especially
for propylene. The MPI won final victory over its opponents and
their respective patent licensees by Civil Action No. 3952 in the
case of the Studiengesellschaft Kohle (a legal arm of the MPI)
against Dart Industries in the U.S. District Court for the District
of Delaware on October 5, 1982.28 This most complex and
labyrinthine series of lawsuits leading up to this definitive
decision has been described in great legal detail by Martin in 2002
and is possibly best appreciated by experienced patent lawyers.29
Guenther Wilke mentioned to me in 1956 how distracting from
genuine scientific research was the experimentation Ziegler and
co-workers had to carry out in legal defense of his patents. Heinz
Martin documents in this monograph how extensive, detailed,
and well documented such lab work had to be in these many
litigations. Such copious defensive experimentation to strength-
en a patent application or to undermine an opponent’s patent Figure 11. Guenther Wilke’s Baracke group. Seated, from left: Peter
was another reason that industrial chemistry seemed to me to be Borner, postdoctorate, Schering Corporation; Hans Breil, chief associate
a melancholy career. with Ziegler in discovering the Mülheim Polyethylene Process; Herbert
Müller, first doctoral student with Wilke, who explored the reactions of
IV. MY RESEARCH ON GALLIUM AND INDIUM aluminum alkyls with acetylenes. Standing: Guenther Wilke (third
ALKYLS person from left), doctoral students, and laboratory technicians
(Laboranten).
A. Preconceptions and Expectations. The 1 year
residency at the MPI was my first, and last, experience of
working at an industry-oriented research laboratory, whose The last two were also especially congenial in after-hours activities,
investigations were aimed at important proprietary chemical such as Karneval parties and excursions.
processes. Even though Karl Ziegler had always attacked the After my meeting with Professor Ziegler on the theme of my
most fundamental problems of organic chemistry, be it C−C research, gallium and indium alkyls, I learned from others at
bond formation, its strength or its mode of rupture, free radicals, the MPI that absolutely no prior work with such alkyls
cationic or halonium ions, carbanions, carbocyclic rings, had been performed at the MPI and that the mention of such
polymerization, or natural products, he kept a steady eye focused alkyls in previous Ziegler patent applications was simply of a
on the organic’s commercial value and utility throughout all his “prophetic” nature. When I began my gallium research there
research. Many of his discoveries early and late in his career found was obvious concern whether or not gallium alkyls would
their way into important patents. Especially at the MPI his surpass aluminum alkyls in their cocatalytic effect in ethylene
extensive cadre of co-workers, staff members, and postdoctorates polymerization. This concern was evident when I first syn-
(Assistenten) such as myself and doctoral students (through thesized pure triethylgallium (Figure 12). With Wilke’s con-
the University of Aachen) worked studiously on data for currence the MPI catalyst group obtained a sample of our
strengthening patent applications. As a necessary consequence, triethylgallium, while I was away on brief vacation, and tested
much proprietary research was not shared with a temporary it in the standard ethylene polymerization procedure used for
outsider like me. Nevertheless, I was kept informed of enough of triethylaluminum. At the time I was upset by this action, but I
such secret work to help my own endeavors. Especially helpful came to realize that Ziegler had a proprietary right to this
were my direct advisor, Guenther Wilke, as well as research information. However, I was never informed of the results of
associates such as Roland Köster and Hans Breil, all of whom their comparative runs.
were members of our Kegelklub (nine-pin bowling club), and Had the polymerization group waited for my testing results, I
postdoctorates Wilhelm Neumann and Peter Borner (Figure 11). could have told them that Et3Ga showed activity comparable to
4925 dx.doi.org/10.1021/om300349x | Organometallics 2012, 31, 4917−4932
Organometallics
Figure 12. John Eisch at the laboratory bench in the Baracke. Setting up
a glass reaction apparatus, at a point where the mandatory eye protection
was not yet required.
that of Et3Al in such TiCl4/Et3M polymerization procedures30
and, as a bonus in information, Et3In had about one-tenth the
activity. The cost of utilizing Et3Ga in place of Et3Al in ethylene
polymerization thus made it prohibitive in commercial ethylene
polymerization, but its comparable activity provided a clue, not
immediately discerned by me, to the likely reaction mechanism.
From my background with my awareness of Gilman’s
empirical reactivity trends, I was from the start pessimistic
about my research project. Gilman and Jones had found that, in
additions to various carbonyl substrates, Ph3Al was decidedly
more reactive than Ph3Ga or Ph3In. In further comparisons
Ph3Ga was sometimes slightly more reactive than Ph3In (with
benzoyl chloride) and sometimes less reactive (with benzaldehyde).
In any event, in such approximate reactivity rankings the order
was clearly Al ≫ Ga ≅ In > Tl.31,32 Naturally, therefore, I expected
that gallium and indium alkyls would be slower in additions to
α-olefin than Et3Al, and their greater cost would make gallium and
indium alkyls poor competitors. Furthermore, in covalent radius,
electronegativity, and C−M bond strength, I saw little promise in
gallium or indium alkyls being superior substitutes in Ziegler
aluminum chemistry. In any discussions I had with the German
doctoral or postdoctoral staff, I noticed that their knowledge of
4926
Review
factual organic chemistry, embracing principally name reactions,
together with their scope and limitations, generally surpassed what I
had acquired in my graduate studies at Iowa State. In contrast,
however, I was surprised at their lack of knowledge of modern
structural and reaction mechanistic theory, which I would summarize
as Erich Hückel−C.K. Ingold−Paul Bartlett−Saul Winstein physical
organic chemistry. When one considers, however, that the first up-to-
date advanced organic chemistry monograph, published in German,
the second edition of Eugen Müller’s Neuere Anschauungen der
Organischen Chemie, containing explanations of molecular orbital
theory and detailed homolytic and heterolytic reaction mechanisms,
appeared as late as 1957, it is no surprise that German doctoral training
had not yet caught up with such advances in the United States.
B. Differing Approaches to Reaction Research: Empiri-
cal Gathering of the Facts versus the Testing of Molecular
Mechanistic Models. If the question of bond breaking in a
proposed reaction mechanism would arise, they would favor homolysis
to free radicals (path a) rather their heterolysis by polarity (path b) or
single-electron-transfer (SET) rupture (path c) (Scheme 3). In fact, in
Scheme 3
the 1930s German chemists such as Karl Ziegler himself, Georg Wittig,
and Eugen Müller had corroborated Moses Gomberg’s theory of the
trivalent (i.e., free radical) character of the triphenylmethyl group by
synthesizing even more stable (persistent, in modern terms) free
radicals, typified by pentaphenylcyclopentadienyl and 1,1,3,3-tetraphe-
nylallyl.
Despite the research of the Ingold and Winstein groups on the
solvolysis of organic halides or pseudohalides, the older generation
of chemists such as Karl Ziegler, Roger Adams, and Henry Gilman
did not readily accept the intermediacy of ephemeral ions in organic
solvents. However, with organic halide or organoalkali reagents they
would recognize the polarity of the carbon−element bond and the
possibility of the organic compound leading to a cryptocarbonium
or cryptocarbanion fragments, never a free ion, at the moment of
reaction (Kryptoionenreaktionen in Meerwein’s conception). In any
case, Ziegler and Gilman considered that such ionic mechanisms
were fraught with too many assumptions to be useful. In seminar
presentations Gilman would express his reservations about reaction
mechanisms in his usual courtly and thoughtful manner, while in
lectures at MPI Ziegler would bluntly state his disdain for any
detailed theoretical discussion of a novel and little explored reaction.
I can now see the merits in their critical approach: they wanted to
find out what happened in a novel reaction and judged that the
known facts were still too inadequate to determine how it happened
on a molecular level. As a young scientist, I was disappointed that
almost no serious effort was given at the MPI to the rich network of
reaction mechanisms likely involved in Ziegler’s novel organo-
aluminum- and transition-metal-catalyzed olefin and acetylene
oligomerizations and polymerizations. In my time at the MPI I
therefore resolved to begin to gather the facts required for a fruitful
study of their reaction mechanisms.
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Organometallics
One nagging doubt about my ultimate ability to be successful in
such research arose from the necessity of performing kinetic studies
on the heterogeneous reaction mixtures formed in Ziegler’s transi-
tion-metal-catalyzed olefin polymerizations. Such studies were
beyond my competence and would, in my opinion then, have
yielded only empirical, ad hoc data capable of evaluating the polymer
productivity of a specific polymerization reactor of a given volume and
configuration. Avoidance of heterogeniety and attainment of kinetics
on the molecular level were not to be solved until the availability of
practical soluble metallocene catalyst systems after 1975.
C. Preparation and Properties of Gallium and Indium
Alkyls. Since I was given complete freedom in my line of
investigation, I decided to make a careful comparison of the
known Ziegler organoaluminum chemistry with that of the
analogous organogallium and organoindium alkyls. By noting the
trend of chemical properties in the congeneric triad of R3Al, R3Ga,
and R3In, I hoped to gain insight into the role of such alkyls into their
reactions with olefins alone and thereafter with olefins combined with
titanium(IV) chloride. Since the most interesting organoaluminum
derivatives were of the types Et3Al, iBu3Al, iBu2AlH, R2AlCl, and
R2Al−OR′, I set out by attempting to prepare the gallium and indium
analogues by known conventional methods. The strong tendency of
almost all organoaluminum compounds to coordinate with ethers or
other donor solvents dictated that any preparation of the gallium or
indium alkyls or salts be conducted in hydrocarbons. Although ether
complexation with gallium or indium alkyls was weaker, obtaining the
unsolvated R3Ga and R3In from ether solution presented difficulties.
Because metallic gallium and indium were convenient starting
materials, the first step was the treatment of the metal in an
evacuated flask with dry Cl2. With gallium a immediate
combustion of the metal globule into flame led to the deposition
of GaCl3 on the cooler wall (eq 10). This organic chemist had
never before witnessed such burning without oxygen!
2Ga + 3Cl 2 ⎯⎯⎯⎯→ Ga 2Cl 6
−ΔH (10)
Instead of using a Grignard reagent (containing ether) or
organolithium reagents (in the 1950s not easily prepared in hydro-
carbons (eq 2), I availed myself of triethylaluminum and triiso-
butylaluminum, both readily accessible in the MPI. Two complic-
ations arose from using R3Al, however. (1) Only one alkyl group of
R3Al was exchangeable in the transmetalation (eq 11):
(in theory)
3Et3Al + GaCl3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Et3Ga + 3Et 2AlCl (11)
(2) Even at the 3:1 ratio of Et3Al and GaCl3, the isolated yield of
Et3Ga approached but did not exceed 50%. In discussions with
Roland Köster he suggested that the strongly Lewis acidic Et2AlCl
coordinated with each of the polarized Ga−Cl bonds to form a
complex (eq 12), tying up half of the GaCl3.
3Et3AlCl + GaCl3 → Ga[AlEt 2Cl 2]3 (12)
In order to set free the GaCl3 and bind the Et2AlCl, the
reaction in eq 11 was repeated in the presence of 3 equiv of
powdered and dry KCl. In so doing, the yield of Et3Ga rose from
42% without KCl to 84% with KCl. The liberation of the
complexed GaCl3 is conceived as in eq 13.
Ga[AlEt 2Al 2]3 + 3KCl → GaCl3 + 3K[AlEt 2Cl 2]
(13)
By appropriate modifications Et3In, Et2Ga, iBu3Ga, and
Et2GaH were accessible in fair to excellent yields. The thermal
stability of this triad of alkyls decreased in the order
4927
Review
R3Al > R3Ga ≫ R3In, with R3In further showing sensitivity to
laboratory fluorescent lighting, which led to indium metal deposition.
In the basic reactions of hydrolysis, oxidation, and Lewis acidity
these gallium and indium derivatives displayed activity distinctly
lessened from that of their aluminum analogues. With either Et3Ga or
Me3In the action of dry air led cleanly to the cleavage of one C−M
bond (Scheme 4), instead of all three with R3Al. Solvolysis with
Scheme 4
ethanol likewise produced the monoethoxyl alkyls. Finally, the metal
trichlorides rank in Lewis acidity in the order AlCl3 ≫ GaCl3 > InCl3.
A striking confirmation of this trend is my observation that even
Et2AlCl behaves as a stronger Lewis acid than GaCl3, as evidenced by
its 3:1 complex with 1 equiv of GaCl3 (eq 12). The distillable, fairly
stable complex 19 is formed by the exothermic admixture of its
components at 25 °C. Although neither the molecular mass nor the
detailed structure was then known, I suggested that each Cl ligand on
Ga behaved as a Lewis base for each Et2AlCl unit (eq 14).
GaCl3 + 3Et 2AlCl ⎯→
⎯ Ga[AlEt 2Cl 2]3
−Δ 19
bp 98 − 102 °C (2.5 mmHg) (14)
The activity trends discussed in the foregoing section are very
similar to those of the reactions of gallium alkyls and alkylgallium
hydrides with olefins. (A parallel study of the possible reactions of
indium alkyls was not undertaken because such alkyls undergo total
decomposition to indium at the requisite temperatures for olefin
interactions.) The temperature required for the olefin displacement
reaction of a 1-alkene with iBu3Ga (eq 15) lies some 50 °C higher
than that for the analogous reaction with iBu3Al.
150 − 160 °C
iBu3Ga + 3H 2CCHR ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Ga(CH 2 − CH 2R)3
−3iC4 H8
(15)
Likewise, the so-called Auf bau or growth reaction of
triethylgallium with ethylene was found to proceed productively
under pressures double that needed for such a reaction with Et3Al
and at temperatures 50−75 °C higher (eq 16).
(CH3CH 2)3 Ga + 3nH 2CCH 2
170 °C
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ [CH3CH 2(CH 2−CH 2)n ]3 Ga
100 − 125 atm (16)
Thus, for the inorganic and organic Ziegler chemistry I
explored in the gallium and indium counterparts, I concluded
that such reactions were too slow, too impractical, or too expensive to
represent a feasible alternative to achieving reactions such as those
found with aluminum alkyls. Such a devaluation in practical
importance also holds for two interesting results discussed in the
next section: namely, the reaction of gallium alkyls with 1-alkynes and
the obvious practical reason for this study, the possible utility of
gallium alkyls as a component with a transition metal salt in olefin
polymerization. However, there I wish to point out the valuable
theoretical implications of our gallium findings to the molecular
mechanisms of Ziegler chemistry.
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Organometallics Review

D. Molecular View of the Properties of Group 13 Scheme 6

Alkyls.33,34 In a discussion of organometallic derivatives of
group 13 it is useful to exclude those of boron and of thallium: the
former because of the low polarity of the carbon−boron bond
and its smaller covalent radius and therewith the magnified steric
effect of ligands and the latter because of the highly screened
nuclear charge on thallium and the much weaker carbon−
thallium bond. The atomic and molecular bonding data of the
remaining triad are given in Table 1. To be borne in mind is the
aforementioned empirical Lewis acidic ranking of MCl3 as
AlCl3 ≫ GaCl3 > InCl3. Of the parameters in Table 1 the only
Table 1. Atomic and Molecular Bonding Parameters of
Aluminum, Gallium, and Indium
property Al Ga In Scheme 7
electronegativity (Allred−Rochow) 1.47 1.82 1.49
covalent radius, Å 1.25 1.26 1.44
atomic radius, Å 1.43 1.22 1.43
ionic radius (+3), Å 0.51 0.62 0.81
ionization energy (3p), eV 6.0 6.0 5.8
mean M−C bond enthalpy, kcal/mol 65.5 59 38

one that correlates qualitatively with such relative Lewis

acidities is the ionic radius. A possible electronic explanation
of this correlation might be that the effective nuclear charge at
ionic radius of 0.51 Å for Al might be the greatest for Al and
determine its greatest attraction for electron pairs of Lewis
bases. I therefore proposed that the greater activity of R3Al
over R3Ga or R3In principally stems from its Lewis acidity
acting on π-basic olefin and acetylenes to form a π-complex-
like transition state (20, Scheme 5), which in turn leads into
the syn adduct 21. A similar explanation would account for
facile hydrometalation of alkynes by iBu3Al or iBuAlH
(Scheme 6). Even though alkynes are weaker π-bases than
alkenes, the transition state for 1-alkenes in carboalumination
and hydroalumination has higher energy steric repulsing
effects in ultimate cis addition (24, Scheme 6), in comparison
with 22.
In such π-complexes as transition states there is an
explanation for the observed difference of reactions between
acetylene and Et3Al or Et3Ga at 25 °C (Scheme 7). The
carbalumination product 23 can readily be accommodated
into the π-complex mechanistic depicted in Schemes 5 and 6
(20 and 22), but the proton−gallium exchange leading to 26
clearly involves a transition state having the gallium center
close to the terminal acetylenic carbon 25 and resembling a
σ-complex. With the known weaker Lewis acidity of Et3Ga, its
π-complex transition state should be of higher energy than
that of aluminum (27). Consequently, it may find a lower
energy transition state bonding to a single carbon: i.e. a
σ-complex. It is noteworthy that the covalent radii of Al and
Ga centers are almost identical, so that no front strain steric
effect is a tenable explanation for the reactions depicted in
Scheme 7.
E. Implications for the Mechanism of Ziegler Olefin
Polymerization. A key observation mentioned at the beginning
of my discussion (vide supra) was a comparative study of the
yields of polyethylene obtained from titanium(IV) chloride
and triethylaluminum according to a published procedure by
Ziegler and Martin for a lecture demonstration. Strictly
according to this procedure but on a 11% scale, I substituted
for the Et3Al, in consecutive reactions, first the equivalent
amount of pure Et3Ga and then that of Et3In. The yields of
polyethylene that a 11% scale of Et3Al (of variable purity)
should have produced was 28−50 g; the yield of polymer
isolated with Et3Ga as the cocatalyst was 47 g and that from
Et3In only 5 g, with traces of In metal. As was to be expected
from our foregoing results, the indium alkyl was essentially
worthless as a substitute for Et3Al. However, what was a
complete surprise was the high activity of Et3Ga, which in this
polymerization procedure was very comparable with that of
Et3Al.
One interesting deduction permissible from this comparative
study is that ethylene insertions in polymerization are not
occurring into carbon−gallium bonds. If such a bond were to be
involved in the rate-determining step, that polymerization would
be slower and less productive. The logical alternative, which
frankly I did not dwell on then, would be that carbon−titanium
bonds must be the sites of ethylene insertions. Early in the
mechanistic studies of Ziegler−Natta polymerization, whether
the carbon−aluminum bond or the carbon−titanium bond was
the active site was still an open question.

Scheme 5

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Organometallics
V. AFTERMATH
With the completion of my 12 month work with gallium and
indium, I was offered an additional year in residence at the
MPI under the Union Carbide Fellowship. Upon reflection I
thought that my wife and now our two small girls were longing
for a return home where the English language and a social life
could be enjoyed again. Moreover, I had declined a generous
offer of a lucrative industrial research position at Union
Carbide and accepted instead an assistant professorship at St.
Louis University, applied for and offered at less than half the
Carbide salary. It took some persuasion to convince my wife
that my attraction for academia meant more to me than
money.
As a compromise, before I left Europe for St. Louis, Union
Carbide offered me a 4 month appointment at their
fundamental research center in Brussels, the European
Research Associates Center mentioned earlier. Top academ-
ically inclined European scientists devoted their time to
pondering industrially important themes, such as Ziegler
olefin polymerizations and Fischer−Tropsch and Roelen
hydrocarbonylations. Situated in an old chateau and within
the most cosmopolitan metropolis in Europe, the ERA was a
most enjoyable environment for science, culture, and a
pleasant social life.
For my first academic position, St. Louis University offered
several appealing aspects: (1) like Marquette, it was a
medium-sized Jesuit-administered institution striving to
improve its graduate programs in the sciences, (2) Professor
George Schaeffer, a doctoral graduate of Herman Schle-
singer’s metal hydride group at the University of Chicago, had
been appointed chair to spearhead such efforts in chemistry,
and (3) promptly Schaeffer set up thriving research on boron
hydrides sponsored by the U.S. Air Force and he judged that
my work with Ziegler would nicely complement his research
efforts. Indeed, in my first year there I was able to start
research on organolithium and aluminum hydride chemistry.
Tragically, by the fall of 1958, however, George Schaeffer was
diagnosed with serious respiratory disease and he passed away
on August 17, 1959, in his early 40s. His promising research
program collapsed, and I was forced to seek and obtain
my next position at the University of Michigan for the fall
of 1959.
Before I had left Mü lheim in April of 1957, I deposited, with
Professor Ziegler, two full manuscripts for intended publica-
tion under his name and with my coauthorship. Upon my
periodic inquiries from abroad I was first informed that
publication would have to await completion of suitable patent
matters. Finally, after about 4 years, when I was at Michigan, I
was informed that Professor Ziegler had decided not to
publish the results under his name and I was now free to do
so independently. Thereafter, I submitted the two manu-
scripts to the Journal of the American Chemical Society, in which
they appeared in 1962.33,34 By that time, I had ascertained
that any fruitful mechanistic studies with group 13 organo-
metallics were best carried out with those of aluminum and
boron rather than with gallium and indium. This unexpected 5
year hiatus in my scientific publication sequence was to cause
me professional difficulties at Michigan, where it was taken
as a sign of particularly unproductive postdoctoral research.
Also, the organic faculty there was unappreciative of my
organometallic research. As one organic colleague jocosely
put it, I was introducing “mighty peculiar elements” into
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organic chemistry. Thus, once finally established at Catholic
University in 1963, my flourishing research in organoalu-
minum and organoboron chemistry made up for this hiatus in
research reports by leading to over 60 publications in my 9
years there.
Epilogue. As a final note, I had avoided undertaking mechani-
stic studies of any Ziegler polymerization catalyst system
because of the difficulty, uncertainties, and pitfalls of
performing reliable kinetic studies in heterogeneous systems.
After the accessibility in 1975 and thereafter of soluble
metallocene procatalysts and main-group alkyl cocatalysts,
such as MAO and perfluorinated boron aryls, the necessary
NMR IR and UV spectral measurements could be made on
the catalyst systems, both by themselves and with a monomer
before polymer began to precipitate. With such favorable
experimental advances, I joined many other academic and
industrial researchers in mapping out the molecular
mechanisms of the organoaluminum chemistry itself and
the related ethylene polymerization and the stereoselective α-
olefin polymerizations.35 Now some 50 years after Ziegler and
Natta’s pioneering and empirical research, it is generally
agreed that the key mechanistic insight into such processes on
a molecular level is the growth of the hydrocarbon chain by
the electrophilic carbometalating attack on the inserting
olefin by an alkylated high-valent transition-metal cation (28
as the proposed transition state, where Cp′ ≠ Cp′′ and M+ is a
chiral center; stereoselective α-olefin insertion may generate
isotactic polymer chains).
The status of the multiple mechanistic insights gained from
such chiral and achiral metallocene-catalyzed olefin polymer-
izations has been superbly and cogently reviewed by leaders in
this research.36 The wide-ranging studies involved in metallocene
synthesis, characterization of catalyst systems, and selectivity in
controlling oligomerization versus polymerization processes
have revolutionized the roles of organic and inorganic chemistry
in modern chemistry and have had an enduring impact on the
textile, petrochemical, materials, and even specialty-chemicals
industries.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jjeisch@binghamton.edu.
Notes
The author declares no competing financial interest.
†
The term “Ziegler-Natta polymerization” in this article is
intended to designate the scientific discoveries involved in this
catalytic process as well as in the structure of the polymers formed
from ethylene, α-olefins, 1,3-alkadienes, or acetylenes. For such
findings the Nobel Prize in Chemistry was jointly awarded to Karl
Ziegler and Giulio Natta in 1963. However, this term does not
dx.doi.org/10.1021/om300349x | Organometallics 2012, 31, 4917−4932
Organometallics
imply anything definitive about the inventorship or patent rights of
such polymerization catalysts (cf. section III.F).
Biography
John Joseph Eisch was born in Milwaukee, Wisconsin, in 1930 and
received his secondary education at St. John Cathedral High School
with concentration on the sciences, mathematics, and Classical Latin.
After graduation as class salutatorian he attended Marquette
University, where he was awarded the B.S. degree in chemistry,
summa cum laude, in 1952. In 1953 he and his former grade school
classmate, Joan Scheuerell, were married and over the years have
raised a family of five, Margaret (dec. 1976), Karla, Joseph, Paula, and
Amelia. After initial studies under scholarship at the Institute of
Paper Chemistry, he thereafter earned the Ph.D. degree from Iowa
State University with Henry Gilman in March 1956 with the
dissertation, “Comparison of Phenanthridine with Other Azaar-
omatic of main-group organometallics (Al, Ga, In) with unsaturated
hydrocarbons at the Max-Planck-Institut fü r Kohlenforschung,
Mü lheim, Germany, and then research fellow at Union Carbide’s
European Research Associates Center in Brussels, Belgium. After
junior appointments at St. Louis University (1957−1959) and the
University of Michigan (1959−1963) and research on such novel
Ziegler organometallic chemistry, he was appointed Associate
Professor in 1963 at the Catholic University of America and there-
after became Ordinary Professor of Chemistry and Department
Head. Finally, in 1972 he was chosen as Chair of Chemistry in the
State University of New York at Binghamton. In 1983 he was
promoted to the SUNY-wide rank of Distinguished Professor of
Chemistry. Over the years he has held visiting appointments at Kyoto
University, Max-Planck-Institut fü r Kohlenforschung, the University
of Munich and the Technical University of Munich, the Polytechnic
University of Warsaw, the California Institute of Technology, the
University of California at San Diego, and Cornell University. He was
named Fellow of the Japan Society for the Promotion of Science in
1979 and has received the first Gilman Research Award from Iowa
State University in 1995 and Alexander von Humboldt Senior
Scientist Awards in 1993 and in 2005. The scholarly work of
Professor Eisch has been devoted to the structures and reaction
mechanisms of organometallic compounds, as well as the chemistry
of fully π-bonded nitrogen and metallocyclic rings. Such research has
involved the fruitful collaboration of over 140 masters, doctoral, and
4930
Review
postdoctoral associates. The results have been reported in over 380
scientific publications, in some 275 invited lectures worldwide, in the
monograph The Chemistry of Organometallic Compounds (Macmillan,
1967), and in the edited series Organometallic Syntheses (J. J. Eisch
and R. B. King, editors). He has been an industrial consultant on
organometallic chemistry and expert witness in several patent
litigations on Ziegler−Natta polymerization catalysis.
■ ACKNOWLEDGMENTS
I thank Dr. Guenther Wilke, my direct mentor during my
postdoctoral fellowship at the Max-Planck-Institut für Kohlen-
forschung in 1956−1957 under the auspices of the former Union
Carbide Corporation. He offered valuable experimental
assistance during the planning and execution of my research.
Moreover, as director of the MPI he extended the hospitality of
the Institut and scientific advice during my periodic residence
over some 35 years. The photographs appearing as Figures 3, 4,
8, 9, and 10 are from the archives of the MPI and appear here
with the written permission of Professor Dr. Matthias W.
Haenel of the MPI. All other photographs in this article are
from my private collection. Furthermore, I thank Jeanne E.
LaBonté for her expert preparation of several printed versions
of this intricate paper. Finally, I gratefully dedicate this article to
the memory of the professors and mentors who aided greatly
in the launching of my career in organometallic chemistry:
Clifford Haymaker, Henry Gilman, and Karl Ziegler. In addition,
I had the pleasure of the friendship and scientific counsel of
Wilhelm Neumann (1926−1993), starting at the MPI after
completing his habilitation thesis on organotin chemistry at
Giessen and continuing at Dortmund as Ordinarius in Organic
Chemistry. Brief biography: Eisch, J. J. Eur. J. Inorg. Chem. 1999,
153−162.
■
REFERENCES
(1) My home basement lab had its start with a small Gilbert
chemistry kit, which was a Christmas gift after my 10th birthday.
Although the scope of the experiments grew widely by the time
of my graduation from Marquette, my father insisted that I stay away
from explosives and flammables such as ether. My experiments
ranged from qualitative identification of inorganics and organics
through food dyes and the pyrolysis products of wood, soft coal and
various plastics. At the time I dismantled my lab in 1952, I was
surprised by the impressive array of chemicals and lab supplies I was
able to donate to my former high school, St. John Cathedral in
Milwaukee.
(2) Eisch, J. J. “Qualitative Identification of the Components of the
Okra Pod Polysaccharide Fraction by Paper Chromatography”, Bachelor
of Science Thesis, Marquette University, 1952, 98 pp, jointly directed by
Professors C. R. Haymaker and K. Brown.
(3) Professor Clifford R. Haymaker, from whom I gained all my
education in organic chemistry while at Marquette, was an
extraordinary teacher and human being. Although he was born
sightless, he pursued his education through high school by tutors,
earning top grades, and then finally obtaining first the B.S. degree in
chemistry and then the Ph.D. in theoretical nuclear chemistry at
Marquette. He taught introductory and advanced organic chemistry
for 30 years at Marquette. A younger colleague and this author have
published a professional appreciation of this remarkable educator
and mentor: Eisch, J. J.; Haworth, D. T. The Professional Career of
Clifford R. Haymaker: A Life of Chemistry Imagined and
Bequeathed. J. Chem. Educ. 2003, 80, 278.
(4) Dr. Kenneth Brown, my introductory organic chemistry laboratory
instructor over two semesters at Marquette, put his experience as an ex-
officer in the Marines during World War II to excellent use in his
teaching style.
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Organometallics
(5) Professor Stephen Darling of Lawrence College and Dr. John
Green of the IPC offered superb lectures on the structures and
properties of organic compounds. The world expert on lignin
chemistry, Dr. Friedrich E. Brauns, maintained a vigorous research
program on the chemistry of wood at the IPC, and I certainly
would have undertaken doctoral research under his guidance had I
stayed.
(6) Frankland, E. Liebigs Ann. Chem. 1849, 71, 171; 1853, 85, 347;
1855, 95, 33.
(7) (a) Historical survey up to 1967: Eisch, J. J. The Chemistry of
Organometallic Compounds; Macmillan; New York, 1957. Historical
survey up to 2005: Elschenbroich, C. Organometallics, 3rd ed.; Wiley-
VCH: Weinheim, Germany, 2006. (b) Providing specific literature
citations for individual aspects of the history and background of
organometallics, such as π-complexes, hydrometalation, etc., would add
unnecessary detail to this review. Instead, the reader is referred to
Elschenbroich’s excellent foregoing monograph for such leading
references.
(8) For scientific evaluations of the career of Henry Gilman: Eisch, J. J.
Henry Gilman (1893−1986): An Appreciation. J. Organomet. Chem.
1988, 338, 281−287. Eisch, J. J. Henry Gilman: American Pioneer in the
Rise of Organometallic Chemistry. Organometallics 2002, 21, 5439−
5463.
(9) (a) Eisch, J. J. “Comparison of Phenanthridine with Other Aza-
Aromatic Heterocycles”, Doctoral Dissertation, Iowa State University,
March 17, 1956, 225 pp. (b) Eisch, J. J.; Gilman, H. The doctoral
dissertation was published under the same title as a review in: Chem. Rev.
1957, 57, 525−581.
(10) (a) Ziegler, K.; Colonius, H. Liebigs Ann. 1930, 479, 135.
(b) Gilman, H.; Zoellner, E. A.; Selby, W. M. J. Am. Chem. Soc. 1932, 54,
1957;(c) 1933, 55, 1252.
(11) Henry Gilman’s more vigorous pursuit of organolithium
chemistry is readily followed because he composed detailed reviews.
(a) Review of lithium−hydrogen exchanges: Gilman, H.; Morton, J. W.,
Jr. Organic Reactions; Adams, R., Ed.; Wiley: New York, 1954; Vol. 8, p
258. (b) Review of lithium−halogen exchanges: Jones, R. G.; Gilman,
H. Organic Reactions; Adams, R., Ed.; Wiley: New York, 1951;
Vol. 6, p 339.
(12) Ziegler, K. Brennst. Chem. 1949, 30, 181 and reference therein.
(13) Ziegler, K.; Gellert, H. G.; Martin, H.; Nagel, K.; Schneider, J.
Liebigs Ann. Chem. 1954, 589, 91 and references therein.
(14) Gillette had been an infrared spectroscopist at the University of
Michigan, who became involved with evaluating German scientific
research carried on during World War II and subsequently became
director of the European Research Associates Laboratory established by
Union Carbide in Brussels after the war. He himself had a strong
attachment to German, especially with a Viennese accent.
(15) The Max-Planck-Institut für Kohlenforschung was founded in
1912 as the Kaiser-Wilhelm Institut für Kohlenforschung, in order to
foster the technical development of the closely connected Rhine-
Westphalia coal and steel industry. The eminent organic chemist and
Nobel Prize recipient Emil Fischer attended the inauguration of the
institute. The first director was Franz Fischer, who developed with Hans
Tropsch the world-famous process for producing hydrocarbons from
carbon monoxide and hydrogen. The name change of KWI to MPI
finally occurred in 1949.
(16) Hammond had received the doctorate with the legendary Paul
Bartlett at Harvard and then established a vigorous program in modern
physical organic chemistry at Iowa State, dealing with free radical
mechanisms, photochemistry, and aromatic substitution and rearrange-
ments. His courses and seminars were open to all and were a great
stimulus to graduate students. Also strengthening the graduate program
was Charles DePuy, who studied with William von Eggers Doering
at Yale and brought to Iowa State an excellent course on Hückel
molecular orbital theory, which was to prove essential for my doctoral
research.9
(17) The most reliable formulations of Gilman’s empirical relative
reactivities of organometallic compounds are given by him in Chapter 5
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in the treatise: Organic Chemistry; Gilman, H., Ed.; Wiley: New York,
1943; Vol. 1, pp 520−524.
(18) As a most compatible complement to my father, my mother,
Gladys née Riordan, was second-generation Irish-American, whose
forebears from County Cork, Ireland, were farmers and school
teachers.
(19) Distinct enclaves of first Germans and then Irish, Italian, and
Polish were formed throughout Milwaukee. Our district of Bay View was
predominantly German before World War II, and our Catholic Church,
St. Augustine, originally had German legends on its walls and stained-
glass windows.
(20) Although our obstetrician had a private clinic, we learned when
Joan had our Karla Maria delivered deep at night on June 13, 1956, that it
was actually a midwife (Hebamme) who would perform the delivery, as
required under German law. The obstetrician could only intervene if
some serious problem were to arise. Joan was surprised indeed by this
unforeseen procedure.
(21) After a 9 day stay at the clinic the mother and baby returned to our
apartment. We had had the baby christened Karla Maria, because I was
fond of the music of Carl Maria von Weber and thought the name very
melodious. When the Zieglers heard about the birth, Professor Ziegler’s
wife, Maria, appeared at our door with a book of German fairy tales.
Then she thanked us for honoring them with the naming of our
daughter. We smiled rather sheepishly but did not have the heart to
reveal the primary reason for her name.
(22) The somber façades of all buildings left standing in Mülheim were
heavily pockmarked from the bombing and yet necessarily were now
provided with new windows and casements. Fortunately, the MPI was
situated on a hill some distance from the city center and escaped
destruction. Our apartment was close to heavy industry so that air
pollution covered all autos with particulate matter. Every morning I had
to wipe off all the windows of my parked Opel. Ironically, the same
pollution created most beautiful sunsets.
(23) Eisch, J. J.; Hordis, C. K. J. Am. Chem. Soc. 1971, 93, 4496−
4502.
(24) Karl Ziegler’s pioneering research on the reactions of olefins
with lithium alkyls and with aluminum alkyls, with or without
transition-metal salts, which culminated in the discovery of the Mülheim
low-pressure polymerization of polyethylene has been presented in
the following reviews: (a) Wilke, G. Liebigs Ann. Chem . 1975, 805−
833 (in German). (b) Eisch, J. J. Karl Ziegler: Master Advocate for the
Unity of Pure and Applied Research. J. Chem. Educ. 1983, 60, 1009−
1014.
(25) Lehmkuhl, H.; Ziegler, K.; Gellert, H. G. In Methoden der
Organischen Chemie; Müller, E., Ed.; Georg Thieme: Stuttgart, Germany,
1970; Vol. 13/4, pp 9−314.
(26) Kharasch, M. S.; Reinmuth, O. Grignard Reactions of Nonmetallic
Substances; Prentice-Hall: New York, 1954; pp 219−221.
(27) Boor, J. J., Jr. Ziegler-Natta Catalysts and Polymerization; Academic
Press: New York, 1979. This book was completed by the staff of the Shell
Development Company after the tragic death of Dr. Boor in an
automobile accident on December 31, 1974.
(28) Civil Action No. 3952 of Studiengesellschaft Kohle vs Dart
Industries, U.S. District Court of the District of Delaware, October 5,
1982. This decision invalidated Dart’s patents on polypropylene and
those of others linked to Natta’s patents from Montecatini. Thereby, the
MPI could legally claim the right to call such olefin polymerization
catalysts “Ziegler catalysts”.
(29) Martin, H. Polymere und Patente (in German); Wiley-VCH:
Weinheim, Germany, 2002; pp 310 ff.
(30) Ziegler, K.; Martin, H. Makromol. Chem. 1956, 18/19,
186−194.
(31) Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1940, 62,
980−982.
(32) Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1940, 62,
2353−2357.
(33) Eisch, J. J. J. Am. Chem. Soc. 1962, 84, 3605−3610.
(34) Eisch, J. J. J. Am. Chem. Soc. 1962, 84, 3830−3836.
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Organometallics Review

(35) Related mechanistic studies by the Eisch group on organoboron-,

organoaluminum-, and titanocene-derived Ziegler olefin polymerization
catalysts has been reviewed, as of 1995, in: Eisch, J. J. Forty Years of
Umpolung in Organometallic Chemistry. J. Organomet. Chem. 1995,
500, 101−115.
(36) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.;
Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143−1170.

4932 dx.doi.org/10.1021/om300349x | Organometallics 2012, 31, 4917−4932