CY6104 :- Molecular cluster

MERIT’S & DEMERIT’S OF WADE’S RULE

Course Coordinator VIPIN KUMAR PANDEY

Dr. S. GHOSH CY17D006
 Contents
 Introduction.
 Wade’s Rule.
 Types of cluster.
 Example of Borane and some other clusters.
 Capping principle.
 Extension of Wade’s Rule.
 Drawbacks of Wade’s Rule.
 CHEMIST KEN WADE
(1932-2014)

Ken Wade developed a method for the prediction of shapes of borane cluster ;
however it may be used for a wide range of substituted boranes as well as other
classes of cluster compound.
 WADE’S RULE
Wade’s rule are used to rationalize the shape of borane clusters by calculating the total number
of skeletal electron pair (SEP) available for cluster bonding.

Structural relationship between closo , nido , &

arachno boranes (and hetero-substituted
boranes).The diagonal lines connect species
that have the same number of skeletal electron
pairs(SEP). Hydrogen atom except those of the
B-H frame work are omitted. The red atom is
omitted first , the green atom removed second.
 Skeletal electron count(X)
For main group metal:- X = v + n -2
For transition metal:- X = v + n – 12
(‘V’ = number of electron given by the metal & ‘n’= number of electron given by the ligand. )
The general methodology to be followed when applying Wade’s rule is as follows:-
1.Determine the total number of valance electrons from the chemical formula.
2.Substract 2 electron for each B-H unit.
3.Divided the number of remaining electrons by 2 to get the number of skeletal electron pair (SEP).
4.A cluster with n vertices (i.e. n boron atoms) & n+1 SEP for bonding has a closo structure.
5.A cluster with (n-1) vertices (i.e. n-1 boron atoms) & n+1 SEP for bonding has a nido structure.
6.A cluster with (n-2) vertices (i.e. n-2 boron atoms) & n+1 SEP for bonding has an arachno structure.
7.A cluster with (n-3) vertices (i.e. n-3 boron atoms) & n+1 SEP for bonding has a hypo structure.
8.If the number of boron atoms (i.e. n) is larger than n+1 SEP then the extra bonding occupies a capping position
on a triangular phase.
 Summary of borane clusters
TYPE FORMULA SKELETAL ELECTRON PAIR

Closo BnHn-2 n+1

Nido BnHn-4 n+2
Arachno BnHn-6 n+3
Hypo BnHn-8 n+4
Klado BnHn-10 n+5

Closo comes from the Greek for cage , Nido the Latin for nest , Arachno the Greek for
spider , Hypo the Greek for net , & klado the Greek for branch.
 Example (boranes)
Structure of B12H12-2

1.Total number of valance electron = 12(B) +12 (H) + 2 = 36+12+2 =50

2.Number of electron for each B-H Unit = 12(BH) = 12(2) = 24
3.Number of skeletal electrons = 50-24 = 26
4.Number of SEP = 26/2 = 13
5.If n+1=13 & n=12 boron atoms, then n=12(number of vertices of the parent polyhedral).
6.Structure of n=12 is Icosahedral, therefore B12H12 is a closo structure based upon a Icosahedral structure.
Continued…
Structure of B5H9

1.Total number of valance electrons = 5(B)+9(H)= 15+9= 24

2.Number of electrons for each B-H unit = 5 (BH) = 10
3.Number of skeletal electrons = 24-10 =14
4.Number of SEP = 14/2 = 7
5.If n+1 = 7 & n-1 = 5 boron atom, then n=6 (number of vertices of the parent polyhedral).
6.Structure of n=6 is octahedral, therefore B5H9 is a nido structure based upon an octahedral structure with
one apex missing.
Continued…
Structure of B5H11

1.Total number of valance electrons = 5(B)+11(H)= 5(3)+11(1)=15+11=26

2.Number of electron for each B-H unit = 5(BH) = 5(2) = 10
3.Number of skeletal electrons = 26-10 = 16
4.Number of SEP = 16/2 = 8
5.If n+1 = 8 & n-2 = 5 boron atoms, then n= 7(number of vertices of the parent polyhedral).
6.Structure of n=7 is pentagonal bipyramid, therefore B5H11 is an arachno based upon a pentagonal
bipyramid with two apexes missing.
Carborane
Structure of C3B3H7

1.Skeletal electron count = 3(CH)+3(BH)+H = 3(3)+3(2)+1 = 16

2. Skeletal electron pair (SEP) = 16/2 = 8
3.If n+1=8 & n-1=6 vertices , then n=7(number of vertices of the parent polyhedral)
4.Structure of n=7 is a pentagonal bipyramid , therefore C3B3H7 is a nido based upon a pentagonal bipyramid
with one apex missing.
Metalloborane
Structure of Mn(CO)4B3H8

1.Total number of valance electron = Mn(CO)4 + 3(BH) + 5(H)

= (7+8-12) +3(2) + 5(1) = 3+6+5 = 14
2.Number of SEP = 14/2 = 7
3.If n+1 = 7 & n-2 = 4 vertices, then n=6 (number of vertex of the parent polyhedral)
4.Structure of n=6 is a octahedral, therefore Mn(CO)4B3H8 is a arachno based upon a pentagonal bipyramid with
two apexes is missing.
Metallocarborane
Structure of CpRhC2B9H11

1.Total number of valance electron = CpRh + 2(CH) + 9(BH)

= (5+9-12) +2(3) +9(2) = 2+6+18 = 26
2.Number of SEP = 26/2 = 13
3.If n+1 =13 & n=12 vertices, then n=12(number of vertex of the parent polyhedral)
4.Structure of n=12 is a Icosahedral, therefore CpRhC2B9H11 is a closo based upon a Icosahedral.
Zintl Ion
Structure of (Ge9)-4

1.Ge is a 3- orbital 2- electron fragment.

2.Total electron = 9 (Ge) +4
= 9 (4-2) +4 = 18+4 = 22
3.Number of SEP = 22/2 = 11
4.If n+1 = 11 & n-1 = 9 vertices , then n= 10(number of vertex of the parent polyhedral).
5.Structure of n=10 is a bicapped square antiprism, therefore (Ge9)-4 is a nido based upon a bicapped square
antiprism with one apex missing.
 Capping principle
Let’s take an example of Os6(CO)18
1.Skeletal electron count = 6(Os(CO)3)
= 6(8+6-12) = 6(2) = 12
2.Number of SEP = 12/2 = 6
3.If n+1 = 6 ,therefore n=5 (vertices of the parent polyhedral, however. we have 6 Osmium centre. Therefore , the
6 Osmium occupies a capped position on a trigonal bipyramid.
Extension of Wade’s Rule
With the help of isolobal analogy a particular fragment in a cluster can be replaced with its isolobal counter part ,
thus extending the Wade’s rule to other substituted borane cluster.

Heteroatom Replace with

C, Si, Ge, Sn BH

N, P, As BH2

S, Se BH3

These represent the most common main group heteroatoms incorporated into hydro borane cluster.
Isolobal vertex unit
The isolobal analogy could also be extended for isolobal transitions metal units.
For example:- B5H9
1. SEP for BH unit = 3+1-2 = 2
2. SEP for CpCo unit = 5+9-12 = 2
Therefore , a BH unit can be replaced by CpCo.
DRAWBACKS OF WADE’S RULE
1.Wade’s Rule can predict the shape of the molecule however it does not predict the geometry.
2.In presence of substituents such as halogen’s or amino group which can meet the electronic demands of boron by
means of back bonding , Wade’s structural scheme is violated.
• The heterocycle C4H4B2F2 has a planar structure rather than a nido structure , the latter being predicted by wade’s
rule. (C4H4B2F2 is isoelectronic with C4B2H6).
C4B2H6:-
 Skeletal electron count = 4(CH) +2(BH) = 4(3) +2(2) = 16
 SEP = 16/2 = 8
 If n+1 = 8 & n-1=6 boron atoms , then n=7(number of vertices of parent polyhedral)
 Structure of n=7 is a pentagonal bipyramid therefore C4B2H6 is a nido based upon a pentagonal bipyramid with one apex
missing i.e. pentagonal pyramidal.
Continued…
3.Wade’s rule could not be justified in case of condensed polyhedral. Hence, Mingo’s fusion formalism came into the
picture.

B20H16
 SEP = n+1 = 21 (closo)
 16 BH unit = 16(2) = 32
 4 B unit = 4(3) = 12
 SEP = 44/2 = 22

According to this , charge of the molecule = +2 , But the molecule is neutral. Hence mno rule came forward to explain
electron counting.
References

1. Chemistry of the elements by N.N.GREENWOOD & A. EARNSHAW.

2. K. Wade , J.Chem.Soc.D. , 1971 , 792.
3. R . W . Rudolph , Acc. Chem. Res. ,1976 , 9 , 446.
4. A. J. Welch , chem. Commun. , 2013 , 49 , 3615.