STEREOCHEMISTRY

UNIT 1B STEREOCHEMISTRY

LESSON STRUCTURE
1B.0 Objective
1B.1 Introduction
1B.2 Electron Deficiency in Boranes
1B.3 Structural Aspects in Boranes
1B.4 Wade’s Rule
1B.5 Carboranes
1B.6 Metal–Metal Multiple Bonding
1B.7 Summary
1B.8 Questions for Exercise
1B.9 Suggested Readings

1B.0 Objective
The studies of Boranes, which are compounds of Boron and Hydrogen has
helped the chemists to understand the principles of chemical bonding and
structure. The study of Boranes also open a versatile and extensive reaction
chemistry.

1B.1 Introduction
Although B does not combine directly with H, a number of hydrides of
B are known. These hydrides are covalent compounds and also called Boranes
by analogy with alkanes. These are electron deficient compounds.
The 1976 Nobel Prize in chemistry was awarded to W.N.Lipscomb for his
studies of Boranes.
Carboranes are derived from BnHn2– by replacing BH– by isoelectronic and
isostructural CH. It's structure can be explained on the basis of the structure
of Boranes.
Wade’s Rule gives a corelation between the number of electrons, the
formula and the shape of the molecule.
Metal–metal multiple bonds follow the same symmetry as those in organic
chemistry.

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1B.2 Electron Deficient Compounds–Boranes

Electron deficient compunds are those in which the total number of atomic
orbitals available on all the atoms of the compound is more than the total
number of valence shell electrons. Or in other words, the molecules which do
not contain enough electrons to form two electron covalent bonds between all
the atoms are called electron deficient molecules.
Examples–
(1) B2H 6
There are 12 valence electrons (6 from 2 B atom, and 6 H atom) but needs
14 electrons to form covalent bonds.
(2) Al 2Cl 3
There are 6 valence electrons from 2 Al and 6 electrons from 6 Cl, but
needs more than that.
Boron combines with HYdrogen to form a number of boranes. As BH3, is
not formed, the simplest borane is diborance B2H6. This is an electron deficient
molecule. The evidence of bond lengths and angles, the infrared stretching
frequency suggest that the terminal B–H are normal single bonds. The two
bridging H atoms are formed as 2e–3C bonds. The three A.Os of 2B and 1H
combine to form one bonding, one nonbonding and one antibonding M.Os.
H H H

B B
H H H

+
+ H +
– – bonding
B B

+
+ H –
non bond-
B B ing
+
– H –
antibonding
+ +
B B

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 terminal

  bridge

 nb

 bridge

 terminal

A.O. of B + B A.O. of 6H

M.O. of B2H6

Molecular Orbital diagram of diborane

About 25 neutral Boranes and a large number of Borane anions are known
to be present.

Other examples of electron deficient compounds are berelium dialkyls and

aluminium trialkyls.

H H H

C Me
Be Be Be

C Me

H H H

X-ray analysis reveals a chain polymeric structure for dimethyl berylium

Be(Me)2 as shown above.
Me

Al Al

Me Me Me
Aluminium trialkyl Al2Me6 is a dimer which contains two bridging groups
of Me as shown above.

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1B.4 Wade’s Rules

A corelation between the number of electrons, the formula and the shape
of the molecule was established by the British Chemist Kennath Wade in 1970.
Wade's rule apply to a class of polyhedra called deltahedra. A deltahedron is
a polyhedron with all faces that are equilateral triangles. For molecular and
anionic boranes, this rule helps us to predict the general shape of the molecule
or ion from its formula. This rule is extended to other p block clusters and
carboranes as it can be expressed in terms of electrons.
The building block of the deltahedron is BH group. The electrons in the
BH group are ignored, but all the other electrons are counted as they help to
hold the skeleton together. Each B–H bond is a unit. If B atom is attached to
two H atoms, only one is treated as a part of B–H unit.
In B4H10, there are four BH units, Each BH unit makes two electrons
available to the structure. 4 BH unit will contribute 8e and 6e will come from
the remaining 6H atoms, making a total of 14e or 7 pairs of electrons.
H
B H
H H
H B B H

H H B H
H

Two pairs of electrons are used for additional terminal B–H bond. Four
are used for B–H–B bridge and one is used for B–B bond.
According to the Wade's Rule, Boranes of formula BnHn2– with n+1 pairs
of skeletal electrons have a "closo" structure (Greek closo–cage) with a B atom
at each corner of a closed deltahedron. This has no B–H–B bond or B–B bond.
The value of n varies from 5 to 12.

B5H52– –2 B6H62–
H
–2
B BH
BH BH
HB

HB BH
HB BH

B BH
H

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Boron clusters of formula BnHn+4 and n+2 pairs of skeletal electrons have
a "nido" (Lation nido–nest) structure. They are derived from closo borane which
has lost one vetex. This has both B–H–B and B–B bond. e.g. B5H9

H
H
H
H Boron atom
H
H
H
H

In general the thermal stability of nido borance is in between closo borane

and arachno borane.

Borane clusters of the formula BnHn+6 and n+3 skeletal electron pairs are
called “arachno” (Greek-spider) structure. These are regarded as closo borane
less two vertices. They have B–H–B and B–B bond. e.g B4H10

H
H
H H

Boron atom
H H

H H
H H

Most arachno boranes are thermally unstable and highly reactive.

Type Formula Skeletal electron pairs Examples

Closoborane B nH n2– n+1 B5H2–, B6H62–,

B12H122–

Nido borane B nH n+4 n+2 B 2H 6, B 5H 9 ,

B6H10

Arachno borane B nH n+6 n+3 B4H10, B5H11

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In naming neutral boranes, the number of B atom in the molecule is

indidcated with a Lation prefix to borane. The number of H atoms in the
molecule is shown by a number in parenthesis. e.g.

B 2H 6 — diborane (6)

B 5H 9 — pentaborane (9)

B4H10 — tetraborane (10)

B5H11 — pentaborane (11)

Using Wade's rule the structure of [B6H6]2– can be inferred from its formula
and electron count as below.

[B6H6]2– belongs to the closo structure from its formula. From electron
count 6 BH will give 6×2=12 electrons + 2e– from its charge making it to 14.
This is 2(n+1) where n = 6. This number of n + 1 electron pair is characteristic
of closo structure. Thus the structure is an octahedron as below.

BH –2
HB BH
HB BH
BH

Wade’s Rule has been justified by Molecular Orbital calculations. In B6H62–

there is n + 1 skeletal electron pair, a B–H bond utilizes one electron and one
orbital of the B atom, leaving three orbitals and two electrons for the skeletal
bonding. One of these orbital called a radial orbital can be considered to be
a boron sp hybrid.

H
| H
B |
B

Radial Orbital Tangential Orbital

The remaining two B p orbitals , the tangential orbitals are perpendicular

to the radial orbital. The shapes of the 18 symmetry adapted linear combinations
of these 18 orbitals in an octahedral B6H6 cluster.

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E
t 1u
eg
t2g Molecular orbital energy levels of
LUMO t2u the B atom skeletal of B6H62–.

HOMO t2g
t1u

a 1g

The lowest energy a1 g arises from the contributions of all the radial
orbitals, t2g are tangentials orbitals. These constitute the seven bonding orbitals
which are occupied with seven pair of electrons.
The structural correlation between closo, nido and arachno boranes is
based on the fact that clusters with the same number of skeletal electrons are
related by removal of successive BH groups and addition of appropriate number
of electrons and H atoms.

B6H62– –BH B 5H 9 –BH B4H10

closo borane +4H nido borane +2H arachnoborane

The concept of three center two electron bonds developed in connection

with B2H6 was extended to higher boranes by the Noble Prize winner Lipscomb.
The bonding scheme depends on the following:
(i) Terminal 2C–2e B–H bond
(ii) 2C–2e B–B bond
(iii) 3C–2e B–H–B bond (bridge)
(iv) Open 3C–2e B–B–B boron bridge bond

B
B B

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(v) Closed 3C–2C boron bond

B

B B

The valence structures of boranes may be expressed in terms of their “styx”

numbers based on the following code system.

s = number of B–H–B bond

t = number of B–B–B bond

y = number of B–B bond

x = number of BH2 group

Diborane has styx number 2002

H
H H
B B
H H H

B4H10 has styx number 4012

H H
H
B B
H
H H
B B H
H
H
H

B5H9 has styx number 4120

H
H H
B B
H

H B H

B B
H H
H

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B5H11 has styx number 3203

H H
H
B B
H H

H B B B H
H H H

1B.5 Carboranes
Carboranes are large family of clusters with contain both B and C besides
H. These are derived from BnHn2– structures replacing BH– by isoelectronic and
isostructural CH. Replacements of 2BH– by two CH results in neutral closo
structures C2Bn–2Hn.

B10 H14 + 2Et2S B10 H12 (Et2S)2 + H2

nido borane

B10 H12 (Et2S)2 + C2H2  B10 C2 H12 + 2Et2S + H2

closo carborane

H –2 H –1

B C

replacement of BH– by CH

H –2

H H

= C atom
H H
H

Closo B6H6–2 Closo 1, 2, B4 C2 H6

The nomenclature should depict the position of carbon atoms.

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The carboranes follow the Wade’s electron counting rule as in the case
of boranes.

As already mentioned, B 10H 14 the decaborane(14) when heated with

diethyl sulphide and acetylen gives 1.2–B10C2H12

B10H14 + 2Et2S = B10H12(Et2S)2 + H2

B10H12(Et2S)2 + C2H2 = 1,2,B10C2H12 + 2Et2S + H2

1.2. dicraba closo dodecarborane

1, 2-carborane 1, 7-carborane 1, 12 carborane (most stable)

Depending upon the relative position of the two carbon atoms in the
icosahedral frame work, three isomers of B10C2H12 are possible. 1, 2 isomer as
above rearrnuges it self to 1, 7 and 1, 2 isomers on heating as shown above.

1B.6 Metal–Metal Multiple Bonding

Metal–metal bonds are known from a very long tme, but lots of work in
this field has been done in the last fifty years. Metal–metal multiple bonds follow
the same symmetry as those in organic chemistry, then they go one better by
allowing quadruple bond formation. Catenation which was earlier to be thought
only in organic chemistry, has proved very important in Inorganic chemistry.

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2
X–ray diffraction shows that Re2 cl 8 has the structure shown below.
2–
Cl
Cl Cl
Re Cl
Cl Re
Cl
Cl
Cl

The eclipsed structure of the two sets of equatorial Cl– ligands, rather than
the staggered structure, would minimise Vander Waal’s repulsions between the
two sets of ligands. The eclipsed configuration is due to dxy orbitals on each
of two Re atoms. The short Re–Re bond distance of only 2.24 A° is due to the
presence of  bonds between the two atoms. Another example is [W2Cl9]3–
3–
Cl Cl Cl
Cl Cl
W W
Cl
Cl Cl
Cl
Another evidence for the presence of a bond is provided by the electronic
configuration transition at 15,000 cm–1 in the near 1R region. The structure
2
can be assigned to  *   transition. All the bonding orbitals is Re2 cl 8 is filled
as shown below.
*


  

bond order 4.0 3.5

Example [Re 2Cl 8] 2– [MO 2(SO 4) 4] 3–
Qualitative Molecular Orbital diagram for dinuclear Re and Mo compounds.

, the bond order of 4 results from one , two  and one 

2
In Re2 cl 8
bond.
Cu(II) and Cr(II) also form acetate complexes of similar to [Re2Cl8]2– and
[MO 2(SO 4) 4] 3–.

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Among more interesting metal–metal multiple bonded complexes are

hexaalkoso dinuclear W and Mo complexes [M2(OR)6] where M= W, Mo
RO RO

RO M M RO

RO RO
The    bonds are somewhat analogous to C  C as they undergo addition
reactions.
b ROg 3
W  W RO
b g 3
 2 X 2  X 2 RO
b g 3
W — W RO b g 3
X 2 (where X= Cl, Br, I)
Going down in the column of transition metal atoms, the increase in the
Pricniplal Quantum Number leads to the maximum in the radial distribution
function moving farther from the nucleus and consequently the overlaps increase
in the order 5d–5d>4d–4d>3d–3d. This has a large effect on the relative strengths
of metal bonding.

METAL-METAL BONDED d-METAL COMPOUNDS

The origin of , , and  interactions Approximate molecular orbital energy

between tow d-block metal atoms level scheme for the M–M interactions
situated along the z-axis. Only the in tetragonal-prismatic twometal
bonding combinations are shown. clusters.

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1B.7 Summary
The bonding pattern in electron deficient compounds is very interesting
and different. The bonding in Boron hydrides can be approximated by conventional
2C–2e bonds together with 3C–2e bonds.

Boron hydride structures include polyhedral closo compounds and

progressively more open nido and arachno structures. Styx number throughs
light on their structure.

When CH is introduced in place of BH– in a polyhedral borane, the charge

on the resulting carborane is one unit more positive. Carborane anions are very
useful in boron containing organometallic compounds.

The transition metals form a wide range of compounds containing more

than one metal atom. The short metal to metal distance suggest the presence
of multiple metal–metal bonds due to the overlap of  orbitals. The maximum
metal–metal bond order may be five i.e one , two  and two  bonds.

1B.8 Questions for Exercise

1. What are electron deficient compounds ? Give the molecular orbital
description of diborane.

2. Write a short note on Wade’s Rule. Using Wade’s Rule infer the structure
of [B6H6]2– from its formula and from its electron count.

3. (i) Draw structural formula of B4H10 and B5H9

(ii) Suggest styx number of B5H9 and B5H11 and give their IUPAC names.

4. What are boranes ? How are they classified ? Give the structure and
bonding in any four of them.

5. (a) Write a short note on Carboranes.

(b) Draw structures of (1, 2), (1, 7) and (1, 12) dicarsa closo dodecarboranes.

6. Write short note on metal metal multiple bonding giving suitable examples.

7. Using Wade’s rule predict the structures of the following:

(a) B4H10
(b) [B5H5] 2–
(c) B6H10

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8. Draw the structure of diborane and explain its bonding. In what way it
differs from bonding in C2H6 ?
9. Write short notes on the following–
(a) Classification of boranes with examples
(b) Electron deficient compounds with examples.
(c) Wade’s Rule and its applications.
10. How are carboranes related to boranes ? How are carboranes prepared ?

1B.9 Suggested Readings

1. Advanced Inorganic Chemistry by Cotton and Wilkinson
2. Modern Inorganic Chemistry by Mackay and Mackay
3. Inorganic Chemistry by Shriver and Atkins
4. Inorganic Chemistry by Gary Wulfsberg

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