VSEPR theory for 3-centre bonds (Bonding in boranes)

The discovery that the simplest borane had molecular formula B 2H6 and not BH3 proved to be
major headache. Traditionally H – atom was believed to form only one covalent bond. In B 2H6 ,
2H-atoms link or bridge the pair of boron atoms. The use of H-atoms as bridges means that one
electron pair can satisfy the bonding requirements of two boron atoms. Each terminal H -atom
forms a normal two electron bond with a boron atom. Each boron atom then has one electron left
and this is paired with the electron of one of the bridging H-atoms.

Bonding in terms of hybridization concept

According to these concepts, the 4 bonds separated by almost equal angles would correspond to
sp3 hybridisation. Three of the four hybrid orbitals will contain single electrons from the boron
atom. Two of these half-filled orbitals would then be involved in bonding with terminal H-atoms.
This arrangement would leave one empty and one half filled hybrid orbital.

To explain how eight electrons are made up in sp 3 orbital set, consider that the single half-filled
hybrid sp3 orbital of the two borons overlap with each other and with the 1s orbital of a bridging
H-atom at the same time. This arrangement will result in a single orbital that encompasses all
three atoms (a three-centre bond). The orbital is capable of containing two electrons.

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Boranes and boron hydrides are electron deficient and pose a problem for conventional
descriptions of covalent bonding that involves shared electron pairs. The description of bonding
in larger molecules formulated by William Lips Comb involved;

 3-centre-2-electron B – H – B hydrogen bridges

To draw the bonds in boranes, the following general formula was adopted [(BH)pHq+c] whereas
for charged species [(BH)pHq+c]c.

P – number of boron atoms

q+c – additional number of hydrogens

c- charge on the borane

The styx numbers were introduced to aid in electron counting where,

S= number of 3-centre B – H – B bonds

t = number of 3-centre B – B – B bonds

y = number of 2-centre B-B bonds

x = number of BH2 groups

To know how many styx numbers, we have equations of balance

q=s+x for H balance

p=s+t for orbital balance

p – ½ q = t + y for electron balance

Applying equations of balance to a compound of given composition allows us to determine a set

Example

Consider B2H6

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[(BH)pHq+c] = (BH)2H4

From q=s+x 4=s+x

p=s+t 2=s+t

p–½q=t+y 0=t+y

values of styx numbers re got by assumption

s t Y x
4 -2 2 0
3 -1 1 1
2 0 0 2
1 1 -1 3
0 2 -2 4
From the table, solution set for styx numbers is 2002 because a solution set with negative values
is invalid.

So, there are 2BHB 0BBB 0BB 2BH2

Example 2: B4H10

[(BH)pHq+c] = (BH)4H6

From q=s+x 6=s+x

p=s+t 4=s+t

p–½q=t+y 1=t+y

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values of styx numbers re got by assumption

s t Y x
6 -2 3 0
5 -1 2 1
4 0 1 2
3 1 0 3
2 2 -1 4
1 3 -2 5

4BHB 0BBB 1BB 2BH2

3BHB 1BBB 0BB 3BH2

H H

H B B

H H

H H

B B

H H H

Draw structures for B6H10, B5H9

Modifications for charged species

The equations of balance can be applied to treat species of charge, c. If the species is protonated
of if H+ are lost or received then the same formula is applied with some modifications i.e
[(BH)pHq+c]c.

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Equations of balance become

q+c=s+x

p + c = s +t

p – ½ q -c = t + y

Example: B5H52-

[(BH)pHq+c]c= [(BH)5H0]2-

q+c=s+x 0=s+x

p + c = s +t 3=s+t

p – ½ q -c = t + y 6=t+y

s t Y x
0 3 3 0
1 2 4 -1
2 1 5 -2
0BHB 3BBB 3BB 0BH2

Solve equations of balance for B3H6+, B6H11+, B3H8-. Write reasonable structures for such hydride
ions.

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