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The elements at top of the group are hard or refractory network covalent materials, those at bottom are soft metals, as
reflected in their enthalpies of atomization and their melting points. Also, they are hard and soft in terms of their Lewis
acidity in the same order. The latter is correlated with polarizability of the atomic orbitals.
The First I.E. decreases down the group, but there is a minor hiccup at Gallium. Similarly, the electronegativities are do
not decrease smoothly: B 2.04; Al 1.61; Ga 1.81; In 1.78; Tl 2.04. The anomalous position of Gallium figures importantly in
the chemistry of this element, and is a consequence of the Scandide contraction. This is reflected in the electron
configuration of the element: it is the first in the group to have a set of filled d orbitals preceding the valence p orbitals. The
very poor shielding of the d electrons results in a higher-than-expected effective nuclear charge on the valence electrons of
Gallium, and hence its anomalous behaviour. We have already seen that Ga 2 H6 is more stable than the corresponding
aluminum hydride, and in some ways Gallium can act closer to boron than Aluminum does.
A similar effect is observed for Thallium, the first element in Group 13 to have a filled f orbital preceding the valence
orbitals. This is called the Lanthanide contraction. Another important factor, the primary influence of which is to greatly
stabilize the +1 oxidation state of Thallium compared to the group oxidation state of +3, is the inert-pair effect. This is
caused by the greater separation in the energy of the ns and np orbitals on going down the group. Tl3+ is in fact a strong
oxidizing agent (see the Frost diagram previously shown in section 4.3 of these notes.) These underlying energetics will limit
the ability of chemists to prepare analogous compounds down the group, e.g. such as in the preparation of multiple bonds for
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 86
the heavy elements, etc. This inert pair effect operates for all the heavy p-block
elements, whereas the scandide and lanthanide contractions lose their importance with
increasing group number (i.e. with the addition of more valence electrons within the p-
subshell.) A key question for any heavy p-element is as to whether the inert pair is
exercising a stereochemical influence on the structure. In some cases it does, in other it
seems not to.
Our chief focus will be on the element boron, and on attempts to prepare analogues
to boron among the heavier group 13 elements that are not part of the classical chemistry
of these elements.
For laboratory use, it is convenient to purchase these reactive compounds as solutions in donor solvents, most commonly in
ether. Their structures are trigonal planar and monomeric (they do not dimerized in the way the BH3 does.) As an example,
the structure of BBr3 is shown to the right of the table.
The bonding in these trihalides is interesting from two points of view. First, we need to explain that fact that they do not
self-dimerize, although they do form conventional ethane like structures in their adducts with stronger Lewis bases. Related
to this issue is the fact that the relative Lewis acid strength measured for the reaction:
Second, we have so-far not considered MO diagrams for halogen derivatives of the elements, having always chosen either
hydrogen terminal atoms, or alkyl groups that can be approximated as pseudo s orbitals. The only exception has been where
we have deliberately chosen an oxygen terminal atom to form a multiple bond. On the whole, halogen compounds serve only
to complicate MO diagrams, because they carry with them so many “lone-pair”
electrons which are mostly unimportant for bonding, and serve only to clutter up the
MO diagrams. Thus it is important to be able to locate such orbitals for the purpose
of being able to ignore them. However, in many cases one formally lone-pair
orbital on each halogen interacts more strongly with the bonding MO’s, and thus
cannot be ignored from bonding situations. Such is the case for the boron halides.
First consider qualitatively what can happen to the MO diagram of BH3 , which
has an empty a 2 ” orbital corresponding to an unhybridized Boron p orbital. There
will be p orbitals on the halogens that can interact with this orbital to form π-type
bonds. The SAO for three p orbitals which are all perpendicular to the trigonal
plane lead to three combinations; one of these has a2 ” symmetry (note that the figure
in the book reproduced at right is mislabeled as a1 ”, which does not match the
SAO’s provided in the text’s appendices.) Only this orbital is of the correct
symmetry to overlap with the central p orbital. The other two remain non-bonding.
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 87
Also, the hexagonal form has one extremely important difference from graphite, in that in the latter the sheets tend to be
stacked over the center of the holes of the ring below. The difference observed for BN is readily attributed to the difference
in electronegativity of B and N, leading to significant ionic contributions to
bonding between Bδ+ and Nδ– .
The layered structure of hexagonal boron nitride has much shorter bonds
within the layers (1.45 Å) compared to the separation between the layers (3.33 Å).
Like graphite, this sheet structure is a slippery material that can be used as a
lubricant. But while the former is black and a good electrical conductor, BN is
colourless and an electrical insulator. The cubic form is adopted when BN is
heated under high pressure (2000 °C at 60 kbar). Like diamond, the sphalerite
form of BN is an extremely hard material that finds applications as an abrasive in
industrial applications. It is the second hardest of abrasive materials, second only
to diamond itself. The graph at right shows the correlation of hardness of the
material with the lattice enthalpy density. The point for C represents diamond, and
BN the sphalerite modification.
H B H H H
N N
B B
H N H H H
H
H
as a line diagram to keep track of the electrons. Borazine is often called "inorganic benzene", with which it is isoelectronic
and almost isostructural. Its physical properties are extremely similar to those of the unsaturated hydrocarbon. Borazine was
first made in 1926 by Alfred Stock (Germany).
Cl H
H B H H B H
N N NaBH 4 N N
C6H 5Cl140 - 150 °C
3 NH4 Cl + 3 BCl3
- 9 HCl
B B B B
Cl N Cl H N H
H H
CH 3MgBr
- 3 LiCl, 9 H 2
3 NH4Cl + 3 LiBH4 Me
H B H
N N
B B
Me N Me
H
Also shown in this scheme is how the original compound can be derivatized by reaction with suitable nucleophiles. Thus
substituted borazines can be made in this manner. The other substitution pattern, i.e. at N, can also be achieved as follows:
Cl
Me B Me
C6H5Cl 140 - 150 °C Toluene Me3 N N N
3 CH 3NH2 + 3 BCl3 Cl3B-NH2CH3
- 6 HCl - Me 3 NHCl
B B
Cl N Cl
Me
NaBH 4
H - NaCl, B2 H6 R
RLi
Me B Me Me B Me - LiCl
N N N N
B B B B
H N H R N R
Me Me
Such substituted borazines have even closer resemblance in physical properties to the corresponding substituted benzene
compounds. However, the very way that they are made, i.e. by nucleophilic substitution at boron or nitrogen is a strong
indication that borazines have very different chemical reactivity than do the aromatic hydrocarbons. This can be seen more
closely by considering the following reactions of borazines.
H B H H B H
N N N N
HCl H H
B B B B H
H N H H N
Cl
Cl
H H H
(Benzene does not react with HCl at all.)
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 90
H B H H B H
N N Br 2 N N
Br Br
B B B B H
H N H H N
Br
Br
H Br H
(Benzene undergoes aromatic substitution rather than addition.)
C C C
C C
C
O O O O
O O
These reactions suggest that there are both similarities and differences between boranzine and benzene. The formation
of “sandwich” complexes at Cr(0) strongly suggests the presence of a π-system in borazine, as does its odour which is
distinctive for aromatic carbon compounds. Yet the reactivity is very different. We need to consider the bonding in these
fascinating compounds in more detail to be able to understand the factors involved.
Compare benzene:
We can easily calculate the molecular orbitals of borazine using the AM1 method. There are many orbitals, and our approach
is going to be that of ignoring the σ-skeleton entirely. The point group of borazine is D3h , and so the orbital labels used for
this compounds are drawn from that point group.
We contrast our result for borazine with that of benzene, for which the point group is D6h , so that the labels of the MO’s
in the diagram will be different. However, from topological sketches (taking a top view of the atomic p-orbitals), or from the
3D graphs taken from HyperChem, it is easy to recognize the similarity between the MO’s despite the difference in labeling
schemes (see detailed diagram on the next page.)
Borazine is described by the same type of bonding model as benzene, consisting of a σ skeleton of sp 2 hybrid orbitals
and a set of delocalized π orbitals. It is possible to write down the π orbitals using Hückel theory, and the orbital topologies
are the same as for benzene. However, in borazine they are not symmetrical, and the more electronegative N atoms have
larger coefficients for the bonding MO's, while the boron atoms have larger coefficients in the antibonding MO’s. After all,
there are fully 1.06 Pauling units difference in electronegativity between boron and nitrogen (huge, considering that the entire
range in electronegativity values across the whole periodic table is only 3.4 Pauling units!)
Such an unequal distribution of the π electron density reduces the ring π bonding, and renders borazine less aromatic
than benzene. This difference is reflected in the chemistry of borazine, which undergoes addition reactions, during which
electropositive substituents become attached to the nitrogen atoms, electronegative substituents to the boron, e.g. HCl.
Another key feature of the electronic structure of borazine is the much larger separation of the frontier orbitals, with the
HOMO-LUMO gap being twice as large as in benzene. This is the origin of the loss of aromaticity in borazine compared to
that of benzene. It also means that borazines are transparent to UV and visible radiation, whereas the benzene ring is an
important organic chromophore in the UV region of the spectrum.
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 91
2 e” and 2a”
1a 2u 1e1g and
Empty π*-orbitals of benzene
2e2u and 1b 1g
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 92
Borazine analogues
Cy Dip Cy Ph Ph
P P N N P P P P As As
Cy B Cy Dip Al Dip Cy Ga Cy Ph Al Ph Ph Al Ph
Mes 1 Me 2 Ter 3 Mes* 4 Mes* 4
Substituent structures: Reference # in red
Mes = Dip = Ter = Cy = Mes* =
H
H 3C CH 3 Pri iPr Ph Ph H But tBu
H H
H H
H H
CH 3 Ph H H tBu
1. HVR Dias and PP Power, Angewandte Chemie, International Edition in English , 26 (1987) 1270 (B/P)
2. KM Waggoner, H Hope and PP Power, Angewandte Chemie, International Edition in English, 27 (1988) 1699
(Al/N)
3. H Hope, DC Pestana and PP Power, Angewandte Chemie, International Edition in English , 30 (1991) 691 (Ga/P)
1. RJ Wehmschulte and PP Power, J. Am. Chem. Soc., 118 (1996) 791 (Al/P and Al/As)
Of the indicated compounds, only the one coloured blue has a planar structure and shortened bonds (note that the X-ray
structure shows a second view without all the substituent atoms projected below which emphasizes the planarity of the ring;
calculations show that this element combination does lead to some aromatic resonance energy. The other examples are all
non-planar and behave as single-bonded compounds with a lone pair on the Group 15 element, and electron deficiency at the
group 13 element. We can understand this by thinking of the π-bonds in all III/V compounds as being dative π-bonds. As
shown in the following graphic, the lone pair on the Group 15 element can be donated into the empty p orbital on the Group
13 element (leading to double bonds, as in the B/P example), or they can remain on the Group 15 element (as for the Al/P):
Cy Cy Ph
Mes P
⋅⋅
Mes Mes P Mes Mes* P
⋅⋅
Mes*
B B B B Al Al
P: :P P P P: :P
Cy B Cy Cy B Cy Ph Al Ph
Mes Mes Mes*
In an MO context, one can think of all the variables that would favour such dative π-bond formation: compatibility of orbital
size and energy for the different element combinations; steric factors emphasizing the puckered structures, etc. Consistent
with this approach (e.g. if used for borazine itself) is the polar nature of the π-bonds that naturally result from such an
approach.
5.5.1 The three main classes of polyhedral boranes and borohydride anions
The following graphics serve to illustrate some examples of these interesting molecules, presenting first of all a
schematic explaining the interconversion between the structural types, and then representative examples with their IUPAC
names and their point groups. Obviously with such weird shapes, the use of point symmetry groups to label the structures is
essential.
The more closed the structure is, the more it approximates a cage structure of boron atoms, and in fact these closo cages are
found in a variety of allotropes of elemental boron as well as in some boron alloys. The more open the structure, the fewer
direct boron-boron bonds are drawn, and the more bridging hydrogen (two-coordinate hydrogen) atoms there are. However,
we will remember from our detailed consideration of the bonding in diborane that even in apparently bridging boranes, there
is a substantial element of direct boron-boron bonding present. It is the same here. In fact, no matter what the actual
structure (or where the artist chooses to draw “bonds” in these pictures) there is always a substantial amount of bonding
occurring at the dead center of the respective cluster structure. This special feature of cluster bonding is best illustrated using
delocalized MO bonding.
Note also in the top graphic the diagonal relationship between the boranes, with logical relationships connecting an n-
closo with an (n – 1) arachno and an (n – 2) nido cluster. The significance of this relationship will be come clear soon. A
more comprehensive list of the possible boron cage structures, emphasizing just this diagonal link, will be presented a little
later after we have considered Wade’s rules.
• Each building block in the deltahedron is a B–H fragment, bonding to other atoms through boron
• Count the total number of valence electrons, then subtract the 2e– in the B-H bond
• If a boron bears more than one H atom, include the 2e– in the second bond
• Count the resulting number of electrons, and divide by two to get the number of skeletal electron pairs
The skeletal electron pairs hold the cluster together, the cluster being considered to consist of x number of B-H units. In this
view, the bridging hydrogen atoms do not have a structural role; rather they are “pasted” onto the framework as best as they
can fit, and MO calculations bear out this viewpoint as being fairly accurate. If the rules seem arbitrary, they have the
advantage of being very effective.
Consider this example of applying the rules to a specific example, that of B4 H10 . Look back at the last page to re-
establish the connectivity in this molecule. There are six terminal B–H bonds, one each on the central borons, two each on
the end borons. There are 4 bridging hydrogens along the sides of the cluster. Now we apply the rules in a systematic
manner. Each boron takes a single H atom in a B–H unit, whose electrons are considered to be firmly localized, and are
therefore subtracted from the cluster count. The remaining electrons are 7 pair. Hence there must be an assignable usage to
these electrons. First we must accommodate the remaining two terminal B–H bonds. Then there are four bridging H atoms
in 3c,2e bonds, thus four pairs of electrons. The seventh electron pair is used to create a formal B–B bond across the middle
of the structure.
The key parameter, however, remains the number of S.E.P., the electrons that are available in principle for cluster bonding.
Wade’s rules uses this paramter in conjunction with the molecular formu la to define the structural class of borane.
The structure of the closo species can be determined by building the smallest closed polygon with all triangular faces.
Note that the theory does not distinguish between electrons that do and those that do not bind H atoms. But in the closo form
there are not enough places to “stick” hydrogen atoms, so that these always carry a 2– charge. The remaining open structures
do provide room for hydrogen atoms, so that edge-forming or terminal H atoms are stuck on to mop up the excess negative
charge.
The diagonal relationship mentioned above is that the sequence
closo → nido → arachno
exists for clusters with the same number of skeletal electron pairs, and increment to one less boron atom, with
adjustment in electrons and hydrogen atoms as required. The full diagonal relationship is shown on the following diagram by
the diagonal linking lines. Your are strongly encouraged to write out a molecular formula for each of the structures below,
remembering that the larger circles are the boron atoms and the smaller are hydrogen. Remember that the closo forms are
dianionic, the rest neutral. You should also assign the point group of each structure. This is particularly important for the
high symmetry clusters. What is the point group of closo-[B6 H6 ]– ? What about for closo-[B12 H12 ]– ? This is a point group
you have very likely not encountered before, because there are no central atom molecules of the type EX n which have such a
high symmetry.
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 96
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 97
In case your solid-state analytic geometry is not quite as good as required, the following chart reminds you of the structures
and names of common deltahedra. These represent the basic building blocks of all cluster molecules.
A helpful description of this approach that presents a bit more detail than Shriver-Atkins is provided by Housecraft and
Sharpe, and I reproduce their discussion below:
Symmetry allows us to separate the orbitals into radial and tangential components, with the sp hybrids being radial, and
the p orbitals tangential (i.e. along the surface of the deltahedron.) The treatment above only provides the bonding set of
orbitals. In all there are 18 combinations of the radial and tangential orbitals. Some of the resulting MO’s are purely
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 99
tangential, some are purely radial, and the rest are mixtures of the two. Now, let us construct an interaction diagram, using
not the single radial and two tangential orbitals, but the six and twelve that actually exist in the cluster. Then we get the
result in the diagram below. The fragment orbitals are the SAO’s provided by Shriver-Atkins for the octahedral point group.
Although spheres are shown for the radial orbital, it is important to realize that these can just as well be sp hybrids, so long as
they point along the radial direction. In fact, there are two sets of such orbitals, one point in, the other out (the B–H bonding
orbitals.
eg eg
t1g t1g
t2u t2u
radial tangential
(6 orbitals)
t1u (12 orbitals)
t1u
t2g t2g
1t1u
a1g a1g
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 100
There are indeed 7 bonding combinations, and hence 11 antibonding combinations, and we note that this is exactly what
is needed to accommodate 14 cluster electrons to completely fill up the t2g HOMO of the cluster. Note also that once again
the text gets one of their labels wrong. The diagram shown below here is a correction to the one provided by Shriver-Atkins
who mislabel the antibonding t1g orbital as t2g . The topologically correct MO sketches were produced using ISIS-Draw, and
are based on the fragment orbitals shown on the interaction diagram on the previous page.
2–
ENERGY LEVEL DIAGRAM TOPOLOGICAL ORBITAL SKETCHES for [B6H6]
We can also treat the bonding in this complex molecule using HyperChem (AM1
method). In addition to the 18 MO’s shown above, there are a further 12 dealing
with bonding and antibonding components of the six B–H orbitals. In the fully
delocalized MO method, there is not clean separation between the two types of
orbitals. However, one can recognize the six lowest MO’s as predominantly B–H
bonding. Also, many of the orbitals sketched above are recognizable in the AM
output. This is an exercise all students in this class need to do. Notice the very
striking agreement with the correct electron population. If a calculation is done
with an overall 2– charge, electrons fill completely the t2g level and leave the anti-
bonding orbitals empty. The order of the empty orbitals is, however, different.
Chemistry 3810 Lecture Notes Dr. R. T. Boeré Page 101
Now remember that we are talking about boron hydrides, yet they act as acids. The smaller hydrides are indeed
hydridic, and especially the anionic ones. But large boron hydrides are robust molecules with sufficiently robust
bonding that they become very much like hydrocarbons, and the hydrogen atoms are somewhat positively charged. All
of this reflects on the stability of larger boron hydride clusters, and this stability can only be understood in terms of the
electron delocalization that occurs in these clusters.
5.5.7 Heteroboranes
Anionic boron hydrides are excellent ligands for metals, and many derivatives of
especially the transition metals are known. These are bonded through bridging
hydrogen atoms. Of more interest to cluster compounds are metallaboranes where
metals are incorporated into the cluster structure with boron-metal bonds. There are
many examples of this type. One example that illustrates the latter type of cluster is the
closo-[B11 (AlCH3 )H11 ]2– , a direct analogue with a heavier Group 13 element, but that
requires an alkyl group on aluminum to be stable. This cluster is shown in the picture at
right, and can be made by the reaction:
2 [ B11 H13 ] + Al2 Me6 → 2 [ B11 H11 AlMe ]
2− 2−
+ 4CH 4
The picture of the structure clearly shows the relationship of this cluster to the closo-
[B12 H12 ]2– . It turns out that a vast number of mixed boron-element cluster compounds,
and even clusters with no boron at all, have structures that are rationalized by the
application of Wade’s rules. One of the most extensive series of such mixed boron
element clusters are the carboranes. This substitution is based on the isolobal
relationship between a H–B group and a H–C group, but since this is a Group 14
element, there is one more positive charge. Hence CH replaces [BH]– , and you will
immediately see that this has important implications in that anionic boron hydrides can
become neutral carboranes. Thus two carbon substitution of any closo borane anion
results in a neutral closo carborane. The isolobal relationship is illustrated by:
The preparation of one such cluster will serve to illustrate the general principles. First nido-B10 H14 is activated by reaction
with the Lewis base SEt 2 , which displaces bridging hydrogens to form arachno-B10 H12 (SEt 2 )2 . This reactive cluster adds one
equivalent of acetylene to form1,2-closo-[B10 C2 H12 ], which is now a neutral molecule. Heating of this compound in the
absence of oxygen forms at about 500°C the re-arranged isomer 1,7-closo-[B10 C2 H12 ], and further heating to an astounding
700°C further isomerizes the structure to the 1,12-closo-[B10 C2 H12 ] isomer. Survival of molecules at such extreme
temperatures is an indication of remarkable and unusual chemical stability. Structures are shown below.
One of the most interesting applications of these carboranes is a result, oddly enough, of converting them back to anionic
structures. Thus 1,2-closo-[B10 C2 H12 ], despite its high thermal stability, can be partially fragmented by a combination of the
strong bases ethoxide and sodium hydride. The deprotonated compound has the formula Na 2 [B9 C2 H11 ]. The structure of this
compound is shown below in a view that emphasizes the empty orbitals along the rim of five boron and carbon atoms. It is
isolobal to the extremely important cyclopendadienide anion, perhaps the single most important ligand for organometallic
complexes of the metals, being used with transition, main group, and f-elements. [B9 C2 H11 ]2– is a dianion, and for certain
metal ions, it forms stronger bonds than the monoanioic [C5 H5 ]– is capable of.
Even small-ring carbon-boron anionic rings can act as powerful donor ligands to transition metals. For example the
highly negative [B3 C2 H5 ]4– ring has a high tendency to form “multidecker sandwich complexes” with late transition metals
such as cobalt and nickel. The structure of the ring, and two mixed-sandwich complexes of metals are shown. The
hydrocarbon [C5 H5 ]– of lower charge must be placed at the outsides of the sandwich, else the charge cannot be fully
compensated. But in the central layers, the carborane ring readily bonds to two electron deficient metal ions.