Course code: HCH416

Course Title: INORGANIC SYSTEMS AND METAL

CLUSTERS
Part A: Heterocyclic Inorganic Systems

Dr. Paul Mushonga.

Rm 205, Chemistry New Wing
Department of Chemistry
UNIVERSITY OF ZIMBWE

Email: pmushonga@science.uz.ac.zw

Office Hours: Tue 14:00-15:30;

Thu 14:30-15:30
or by appointment.
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MUSH
WADE’S RULES
• The rules pertain to boranes of the formula
[BnHm]x- where mn and x 0

i.e. neutral boranes or anions are considered

• From MO calculations independent of the value of n,
– if m = n and the structure is closo, x must equal z in order
for all bonding orbitals to be filled and for all anti-bonding
orbitals to be empty
There are (n+1) Pairs of Electrons for Skeletal Bonding
(one pair already allocated to each B-H bond

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Consider [B6H6]2-

• Each B-H group supplies three orbitals and 2 electrons to the

octahedral framework

• Atomic orbitals combine to generate 7BMOs and 11 ABMOs

each B supplies 3 – AOs
 total of 18 AOs for the 6 B atoms
 12 e (2x 6 from 6B’s) + 2 e (from charge)  14 e
14/2 BMOs = 7BMOs

• To fill the 7BMOs, one pair of electrons is required hence the

charge of -2 applies to all closo-boranes
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Wade’s Rule # 1

• For a [BnHn]x- species, the preferred structure is a Closo

n-vertexed polyhedron with a charge of 2- (i.e. [BnHn]2- )

• There are then (n+1) Pairs of Framework (Skeletal) Electrons

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Wade’s Rule # 2

• For a BnHn+4 borane, where there are (n+2) Pairs of

Framework Electrons, a NIDO-structure is preferred

• Consider [BnHm]x- species with mn; (there are a number of

these where m = n+4 and x= 0 e.g.
B5H9 and B6H10
• If you remove m-n protons, you will have [BnHn]4-
• Such species [BnHn]4- will have (n+2) Pairs of Framework
Electrons and hence a NIDO-structure
B H ; m = n+4. Now
• n m
remove m-n protons
, remain with m-(m-
n) = n [BnHm]4-

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Wade’s Rule # 3

• For a BnHm borane, based on a [BnHn]6- anion, an

ARACHNO-structure derived from n-2 vertex polyhedron is
preferred.

• It has (n+3) Pairs of Framework (Skeletal) Electrons

• Formula is BnHn+6

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Wade’s Rule # 4

• For a BnHm species that derives from a [BnHn]8- anion, a

HYPHO-structure is preferred.

• It has (n+4) Pairs of Framework (Skeletal) Electrons

• Formula is BnHn+8

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Summary of Structural and Bonding Patterns

TYPE FORMULA SKELETAL EXAMPLES

ELECTRON
PAIRS
Closo [BnHn]2- or n+1 [B5H5]2-
BnHn+2

Nido [BnHn]4- or n+2 B2H6 B5H9

BnHn+4 B6H10

Arachno [BnHn]6- or n+3 B4H10 B5H11

BnHn+6

Hypho [BnHn]8- or n+4

BnHn+8

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Example 4
Count the number of Skeletal electrons in B4H10

Answer:
B4H10 = (BH)4H6
4BH units = (4x2)e = 8e
6H units = (6x1)e = 6e
14e
7 electron pairs = (4+3)  (n+3) electron pairs

The 7 electron pairs are used as follows:

– 4 Pairs for B-H-B bridges
– 2 pairs for additional B-H
– 1 pair for B-B bond
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Using Lipscomb’s STYX notation

• What is the topological representation of B4H10

• Molecule can be formulated as (BH)4H6 c.f. BpHp+q

p=4;q=6
p = s+t; q = s+x; p = t+y+ ½q
4 = s+t 6 = s+x 4 = t+y+3
1 = t+y
Now all numbers must be  0
 For t = 1;  y = 0, s = 3, x = 3  <3103>
For t = 0;  y = 1, s = 4, x = 2  <4012>

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Example 5
Infer the structure of [B6H6]2- from its formula and from its electron
count.

Answer:
(a)
The formula [B6H6]2- belongs to a class of boranes with the
formula [BnHn]2- which characteristic of a Closo-species.

(b)
[B6H6]2- = [(BH)6]2-
6BH units = (6x2)e = 12e
Electrons from overall charge = 2e
Total SKELETAL Electrons 14e
7 electron pairs = (6+1)  (n+1) electron pairs (n = 6) which is
characteristic of CLOSO-structures
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Example 6
Using Wade’s rules, infer the structure of [B5H5]2- from its
electron count. Sketch the structure
Answer:
[B5H5]2- = [(BH)5]2-
5BH units = (5x2)e = 10e
Electrons from overall charge = 2e
Total SKELETAL Electrons 12e
6 electron pairs = (5+1)  (n+1) electron pairs where n
= 5, which is characteristic of CLOSO-structures
The closed polyhedron must contain triangular
faces and 5 vertices  trigonal bipyramidal

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2.2 CARBORANES
• These are cluster compounds containing both boron and
carbon as framework atoms

• CH and BH- are both isoelectronic and isolobal. They both have
one sp- orbital, two p-orbitals and three electrons available for
cluster bonding

• Therefore, in principle, BH- units in a polyhedral borane can be

replaced by CH units without changing the structure

• This generates the series:

[CBn-1Hn]- and [C2Bn-2H5n] equivalent to [BnHn]2-

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2.2.1 Synthesis of Carboranes
• Closo- C2BnHn+2 species are prepared by reactions of
acetylene, RCCH or RCCR’ with a borane, either thermally or
in a silent electric discharge

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2.2.2 Conventional Way of Writing Some Reactions

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• Electron count for C3B3H7

• C3B3H7 = (CH)3(BH)3H

3BH  (3 x 2) = 6e
3CH  (3x3) = 9e
1H  (1x1) = 1e
Total # of electrons for 16e
Cluster Bonding

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Example 7
(a) Rationalize why the cage structure C2B4H6 is an octahedron.
(b) How many cage isomers are possible
Answer:
(a) C2B4H6  (CH)2(BH)4
Valence electrons: 2CH  2x3 = 6e
4BH  4x2 = 8e
Total Valence Electrons 14e
Pairs of Framework Electrons = 7 e pairs
 C2B4H6 has 7 pairs of electrons with which to bond
6 (2CH + 4BH) cluster units
There are (6+1) electron pairs = (n+1) pairs of electrons
for n vertices

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 C2B4H6 is a Closo-cage , OCTAHEDRON adopted
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(b) In the octahedron, all the vertices are equivalent

 Possible cage- isomers are:

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