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CH2201 – Organometallics and Cluster Chemistry of the Main Group Elements

Oligomers and Clusters


An oligomer consists of less than five monomer units, similar to a polymer. A cluster is an ensemble
of bound atoms intermediate in size between a molecule and a bulk solid, there are ‘naked’ clusters
which do not require ligands to provide stabilisation and those with ligands.

Methyl Lithium
Lithium alkyls are important chemically as they are unable to gain the desired number of electrons
to form simple 2 centre, 2 electron bonds and complete the octet. As such bridging ligands and
oligomeric structures are common in solution and in the solid state. In the solid state methyl lithium
is made up of linked (CH3Li)4 tetramers, each a distorted cube with lithium and carbon atoms in
alternate corners.

There is also a hexameric form, again with carbon and lithium atoms on alternate corners as above.

Boron Chemistry – Borane and Diborane


Borane is formed in the reaction of NaBH4 and I2 to form BH3 and NaI. BH3 will dimerise at room
temperature to form diborane, B2H6. Diborane contains 8 bonds, however, if the valence electrons
are totalled (2x3 from Boron, 6x1 from Hydrogen) there are only 12 available electrons in total,
diborane is electron deficient.

Conventional valence bond theory requires two electrons for each bond (i.e. forming 2 centre 2
electron bonds); diborane is therefore 4 electrons short of the necessary number of electrons for its
structure. There are many boron hydrides of the formula B nHm and anionic boranes of the type BnHm-
, these too are electron deficient and as such a new theory of chemical bonding.
Diborane can be cleaved using a strong Lewis acid and the reaction will follow one of two pathways.
The Lewis acid will first form an adduct with a boron atom within diborane, followed by a second,
the position of which determines the products. Either 2BH3L molecules form (homolytic cleavage) or
a BH4- and a BH2L2+ form (heterolytic cleavage). The heterolytic cleavage is the preferred pathway,
potentially due to the ionic stabilisation, if the Lewis acid used is large then stearically the homolytic
pathway can be forced. To determine which products have formed 11B{1H} NMR can be used to show
one peak for the homolytic pathway, or two for the heterolytic pathway.

Diborane will react with BMe3 to form varying degrees of substituted species, from monomethyl
through to tetramethyl (with methyl groups occupying the terminal position), again the products of
this reaction can be recognised using 11B{1H} NMR to differentiate mon/bis from tris/tetra, with
further differentiation possible using 11B NMR.

Diborane can also be thermolysed to form borane clusters, this occurs by loss of H2, loss or gain of
(BH) units and loss or gain of (BH3) units;

i.e.
B2H6⇋{BH3}
B2H6+{BH3}→{B3H9}→{B3H7}
{B2H7}+{BH3}→{B4H10}

Boron hydrides can be prepared by adding acids to metal borides, there are many known natural
and anionic boron hydrides. They form polyhedral structures based on regular polyhedral, possibly
with missing vertices. The polyhedra are made up of B-H units at the vertices, with bridging
hydrogen atoms along the edges in some cases.
The B-H fragment itself consists of an sp hybridised boron atom, one of the sp hybrids points
towards the hydrogen atom and forms bonding and anti-bonding molecular orbitals by overlap with
the hydrogen atoms 1s atomic orbital. The other three orbitals at boron are the other sp hybrid and
two perpendicular 2p atomic orbitals.
To predict the structure of a boron hydride, B nHm, Wade’s rules provide a system for determining
structure based on the number of pairs of electrons available for cluster bonding. These electron
pairs are known as Polyhedral Skeletal Electron Pairs (PSEPs), Wade’s ideas are known as Polyhedral
Skeletal Electron Pair Theory (PSEPT).

To count electrons;

1. Each BH unit donates two electrons (one pair) to cluster bonding


2. Each extra hydrogen donates one electron
3. Any overall charge in the molecule is considered
4. The total number of electrons should be an even number, 2n, therefore there are n PSEP’s
involved in cluster bonding
5. If there are n pairs, the structure is based around a polyhedron with n-1 vertices

If the number of BH units is equal to the number of vertices then a BH unit will occupy each vertex
and the structure is defined as closo. If there is one less BH unit than there are vertices then the
vertex of highest connectivity is left empty, giving a nido structure. If there are two less BH units
than there are vertices then all but two vertices (with those two being adjacent) are occupied, giving
an arachno structure. Remaining hydrogen atoms are then placed in bridging positions around the
open faces as these are the positions with orbitals ‘spare’ with which to bond to the hydrogen
atoms, if there are no face positions open, terminal hydrogen atoms can be placed on boron atoms
with remaining orbitals.

Carboranes
It is possible to replace a boron atom within a boron hydride with a carbon atom, these species are
collectively known as carboranes. These can be formed by reacting a boron hydride with ethane
under heat.
A B-H unit is isoelectronic with C-H+, it has the same 4 electrons with 2 involved in the C-H bond,
meaning C-H+ also has 2 electrons to donate to cluster bonding, if we regard the carbon atom as
being sp hybridised it also has the same orbitals available for cluster bonding as the BH unit, the B-H
and C-H+ unit are said to be isolobal, they have the same number of electrons with frontier orbitals
of the same symmetry and similar energy, as a result of this B-H and C-H+ units are interchangeable
in clusters and Wade’s rules can be used to work out structures of carboranes as before.
A C-H fragment will donate 3 electrons to cluster bonding however the principle remains the same.
Isomerism within carboranes, for example 1,2-C2B4H6 or 1,6-C2B4H6, will depend on thermodynamic
stability, where possible the carbon atoms will be apart in order to maximise the number of C-B
bonds and minimise the number of C-C bonds, at high temperatures 1,2-C2B4H6 will rearrange to give
the more stable 1,6 isomer. In the situation where there is one CH unit it will occupy the position of
lowest connectivity. Also, B-H-B bridges are more thermodynamically than C-H-C bridges, so bridging
hydrogen atoms will always prefer positions in which they bridge two boron atoms. As before, in a
nido structure the vertex of highest connectivity will be unoccupied.
Using Hybridisation to Explain Wade’s Rules
Consider B6H62-, first looking at the individual BH units. The fragments are located at the vertices of
the polyhedron, with the B- bond pointing outwards from the cluster, since each boron is sp
hybridised one of the sp hybrids will point towards the hydrogen to form the bonding and anti-
bonding molecular orbitals with the hydrogen 1s atomic orbital, this leaves a remaining sp hybrid
and two unhybridised p orbitals that are non-bonding. Of these 3 non-bonding orbitals the sp hybrid
orbital is radial, pointing towards the centre of the cluster, the two p orbitals are tangential. In B 6H62-
this will give 6 radial orbitals and 12 tangential orbitals, it is the overlap of these 18 orbitals that
combine to form the molecular orbitals (bonding, anti-bonding and non-bonding) for the cluster,
filling of the molecular orbitals provides the bonding. The 18 orbitals will overlap to give 7 bonding
molecular orbitals and 11 non-bonding and anti-bonding molecular orbitals. For B6H62- there are
therefore 7 PSEP’s required to fill the bonding molecular orbitals in order to occupy an octahedral
geometry. An n vertex polyhedron has n+1 bonding molecular orbitals requiring n+1 PSEP’s.

Using this description, Wade’s rules can be applied to other clusters.


i.e. Germanium, 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
The two electrons in Germaniums 4p2 orbital allow it to donate 2 electrons to cluster bonding, so a
species such as Ge102- will have 10x2 electrons available from 4p orbitals, and 2 for the charge to give
a total of 22, this makes 11 PSEP’s and a 10 vertices polyhedra (a bi-capped square antiprism), in this
case forming a closo structure.

Organometallics of Groups 1 and 2


The organometallic chemistry of group I is dominated by lithium, lithium organometallics are
generally more covalent and more stable than their heavier counterparts, the other elements of
group I give predominantly ionic species which are highly reactive and difficult to isolate.
There are several methods of forming lithium organometallics;

-Direct reaction of the metal with an alkyl or aryl halide


CH3Br + 2Li 20𝑜 𝐶 𝐻2 𝑂 CH3Li + LiBr

-Reaction of a strong lithium containing base with an acidic C-H bond


C5Me5H + nBuLi 𝑇𝐻𝐹−78𝑜 𝐶 C5Me5Li + BuH

-Reaction of an acidic C-H bond with the metal


C5H6 + Na 𝑇𝐻𝐹 C5H5Na + ½H2

-Metal/halide exchange
nBuLi + PhX → nBuX + PhLi
RM + R’X → RX + R‘M

Lithium alkyls, though more covalent than the derivatives of other group I organometallics, cannot
gain enough electrons from simple 2 centre 2 electron bonds to complete the octet. Bridging ligands
and oligomeric structures, as with boranes, are common in solution and in the solid state. Methyl
lithium, MeLi, is madeup of linked (CH3Li)4 tetramers in the solid state, each tetrmer is a distorted
cube with Li and C atoms at alternate corners. The structure is effectively an Li 4 tetrahedron with a
CH3 ligand bonded to each face, however this leaves each Li with only 2 formal electrons in each
LiCH3 unit, this is explained using molecular orbital diagrams.
At each Li3 face of the Li4 tetrahedron there are three orbitals facing outwards overlapping
eachother, one for each lithium atom, these can take different symmetries based on the principal
that the orthogonal orbitals must have an overall overlap of 0. a1 symmetry in which all 3 are in
phase, and two e symmetries, one in which one bonding and one non-bonding orbital protrude and
the second in which one large non-bonding orbital overlaps with two bonding orbitals negating
eachother. The a1 symmetry allows for optimal overlap with the approaching CH3 orbital,
overlapping to give bonding and anti-bonding orbitals, the e combinations are non-bonding.

This provides the following MO diagram;

Anti-bonding

Non-bonding e
a1

sp3

Bonding

For the (CH3Li)4 tetramer there are 8 electrons, therefore 2 per face and in turn 2 to place into the
MO scheme (as shown), this is an example of 4 centre 2 electron bonding, a relatively weak bond
and highly electron deficient (comparative to B2H6). Tert-butyllithium has a similar structure,
[(CH3)3CLi]4, both in solution and in the solid state, proven by 7Li NMR of a sample enriched with 13C.
A septet is obtained, 13C-7Li has a coupling constant, J, equal to 11 Hz, however the observed value of
J in 7Li of tert-butyllithium is 5.5Hz, this shows a composite effect. 13C3-Li will give a quartet, however
13 12
C2 C-Li will give a triplet, 13C12C2-Li will give a doublet and 12C3-Li a singlet, the septet this gives rise
to can be explained using this information;

The first, third, fifth and seventh peak are due to the quartet.
The second, fourth and sixth peak are due to the triplet.
The third and fifth peak are due to the doublet.
The fourth peak is due to the singlet.

Group 2; Grignard Reagents


Grignard reagents can be formed by the reaction of magnesium with an alkyl halide;
Mg + RX 𝐸𝑡2 𝑂 RMgX(Et2O)n
Where X=Br, I

In solution Grignard reagents undergo the Schlenk equilibrium;

This equilibrium can be shown by room temperature 1H NMR, only one Me signal is seen, however at
-100oC several peaks appear, similarly for 25Mg NMR, this shows that in reality the situation is even
more complicated.
In solvent the magnesium is ligated so that it is always tetrahedral, an equimolar mixture of MgX 2
and MgR2 in ether will behave identical to a prepared RMgX Grignard reagent.

Organometallics of Group XIII


The bonding in group XIII organometallics is predominantly covalent (except for some Al derivatives
which show more ionic character) with the +3 oxidation state most common, with some sub-valent
species in the +1 oxidation state (due to the inert pair effect), the stability of the +1 oxidation state
increases down the group.

BMe3 can be prepared by reaction of BF3.OEt2 and 3RMgX, forming BR3 and 3MgFX. BMe3 is planar
and monomeric, this is true for all group XIII analogous structures except for Al2Me6.

Trimethyl aluminium takes a dimeric structure with symmetrical methyl bridges, the NMR of
trimethyl aluminium shows one methyl signal in both 1H and 13C at room temperature but at -40oC
two signals (ratio 2:1) are seen. This is due to interconversion of bridging and terminal methyl
ligands via a mono-bridged species at room temperature, only when the temperature is lowered
enough to prevent this interconversion do the methyl groups cease to be equivalent. The bonding of
the bridging methyl groups is of the 3 centre 2 electron type (as in B2H6). Symmetric combination of
the sp3 hybrids at each Al centre is the same symmetry as the sp 3 hybrid at carbon, these overlap to
five bonding and anti-bonding MOs, the anti-symmetric combination remains non-bonding.

Anti-bonding

Non-bonding e
a1

sp3

Bonding
The methyl derivatives of gallium and indium, GaMe3 and InMe3 are known, however they are
monomeric in solution.

Multiple Bonding in Group XIV


C=C bonds have been known for centuries, however it was believed for a long time that multiple
bonds involving heavier elements (e.g. Si=C or Si=Si) were thought impossible, due to poor p orbital
overlap. The first Si=Si bond synthesised was by West in 1981, using mesityl groups (2,4,6-Me3C6H2,
very bulky) as protecting groups. d(Si=Si)=2.15 angstroms compared to 2.35 angstroms for the single
bond however the framework is bent, only the mesityl groups provide stabilisation
thermodynamically and kinetically.
Sn=Sn bonds are also known, in distannylenes, and can be formed by;

SnX2 + 2RLi → R2Sn: (a carbene analogue) where R is -C(SiMe3)2H


This species then dimerises to form the distannylene with a bond distance of 2.76 angstroms
(compared to 2.77 angstroms for the single bond). This, shorter than expected, bond length can be
explained as being due to a two way donor/acceptor bond, it also explains the 41 o angle observed as
the R group is shifted from the plane, each tin atom donates two electrons into an empty orbital on
the other. The trend for this behaviour increases down the group due to orbital stability, the s orbital
is greater stabilised than the p orbital in the lower elements making it more favourable than
hybridised alternatives.