Valence Bond Theory

By Prof Yeap Guan Yeow

The knowledge on complex formation from the reaction between the donor and acceptor properties was developed by Linus Pauling to become valence bond theory (VBT) This basic concept involves donation of electron pairs from the donor atom to the empty orbital (d orbitals) of metallic ion. This phenomenon is encouraged via the hybridization of valence atomic orbitals within the metal atom leading to a set of equivalent orbitals which receives the electron pairs from the donor atom.

As a result, the structure for transition metal complexes can be stabilized through different types of orbital hybridization of metallic atom as shown in the following structure .

Hybridization sp, ds sp2 sp3 , d3s dsp2 dsp3, d2sp2 , sp3d sp3d2, d2sp3

Structure linear trigonal planar tetrahedral square planar trigonal bipyramidal octahedral

(a) Ni(CO) 4 Ni(0) Ni(CO)4 [Ar]3d84s2

xx x x xx xx

sp3

The above suggest that all electrons are paired and that the magnetic moment, = 0. It means that the Ni(CO)4 complex is diamagnetic. The structure of molecule for the Ni(CO)4 complex can be shown as follows:

O C Ni C C C O
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(b) [Ti(H2O)6 ]3+

O O H2 H2 O H2 O O O H2 H 2 H2

- Paramagnetic property - Orbital hybridization d 2sp3 (octahedral)

Magnetic moment, ? = Since, n = 1 therefore, ? = B. M.

B. M.

Ti(O) 3d2 4s2 Ti(III) 3d1

In order to predict the actual molecular structure, the value is needed. To understand this fact, try to refer to the [Co(NH3)6]3+ and [CoF6]3- complexes.

For [Co(NH3)6]3+

XX XX

XX
d2sp3

XX XX XX

=0

diamagnetic

[CoF6]3XX XX XX XX XX XX

sp3d2 = 5.9. B.M. paramagnetic

The difference in above complexes can be explained by the outer and inner orbital complex concept.

In this context, d2sp3 and sp3d2 are thought to have the same energy. Every orbital is resulted from the hybridization of the s, p and d orbitals leading to d2sp3 and sp3d2 respectively. (i) For sp3d2 hybridization: 4s, 4p and 4d orbitals are close in energy levels. (Outer orbital complex) (ii) For d2sp3 hybridization: 3d, 4s and 4p orbitals are close in energy levels. (Inner orbital complex)

The weakness of valence bond theory (i) The assumption that all 3d orbitals have the same energy contradicts with other theories.

(ii) The use of 3d and 4s orbitals with different energy to form the chemical bonding is unsatisfactory. (iii) This theory does not explain the electronic spectra which are caused by the transition of electrons between the d orbital levels. (iv) This theory cannot predict the electronic spectra which are caused by the transition of electrons between the orbital levels (degenerate).

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For example, Ni(CN)42 d8 =0 diamagnetic ! Ni(CN)3d9 =0 diamagnetic

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According to valence bond theory;

Ni(CN)4 2Ni(CN) 3 -

0 0

0 0

0 0

0 0

? = 0 ; diamagnetic

d sp2
0 0 0 0 0 0 0 0

sp 3

? = = = 1.7 B.M Paramagnetic

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Ni(CN)3- complex which is a monomer can adopts a paramagnetic properties if based on the value of . However, in practical it is found to have diamagnetic properties. This observation suggests that there are changes occurred in that complex. One of the probability is the dimer transformation as shown in the following scheme Ni(CN)3- ! ! Ni2(CN)62- . This phenomenon can be stabilized by using dsp2 orbital.

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Ni

Ni

Ni-Ni bond formation. As a result, = 0 diamagnetic ; Ni(CN)3- complex is diamagnetic.

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dz2 and dx2-y2 orbitals have the charge density which is directed to (i) z axis , (ii) x and y axis, respectively.

The dxy, dxz, and dyz orbitals will not direct themselves accurately on the Cartes axes; that is to say, the lobes for the three orbitals are placed 45 in between the axes.

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