Valence Bond Theory (VB)

Many approaches have been put forth to explain the nature of bonding in coordination compounds. One of them is the Valence Bond (VB) Theory. The Valence Bond Theory was developed in order to explain chemical bonding using the method of quantum mechanics. This theory primarily focuses on the formation of individual bonds from the atomic orbitals of the participating atoms during the formation of a molecule.

What is Valance Bond (VB) Theory?

According to the valence bond theory,

Electrons in a molecule occupy atomic orbitals rather than molecular orbitals. The overlapping of atomic orbitals results in the formation of a chemical bond and the electrons are localized in the bond region due to overlapping.

The metal bonding is essentially covalent in origin and metallic structure involves resonance of electron-pair bonds between each atom and its neighbors.

Table of Contents

• History of Valence Bond Theory
• Postulates of Valence Bond Theory
• Number of Orbitals and Types of Hybridization
• Applications of Valence Bond Theory
• Limitations of Valence Bond Theory
• Solved Example

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History of Valence Bond Theory

The Lewis approach to chemical bonding failed to shed light on the formation of chemical bonds. Also, valence shell electron pair repulsion theory (or VSEPR theory) had limited applications (and also failed in predicting the geometry corresponding to complex molecules).

In order to address these issues, the valence bond theory was put forth by the German physicists Walter Heinrich Heitler and Fritz Wolfgang London. The Schrodinger wave equation was also used to explain the formation of a covalent bond between two hydrogen atoms. The chemical bonding of two hydrogen atoms as per the valence bond theory is illustrated below.

This theory focuses on the concepts of electronic configuration, atomic orbitals (and their overlapping), and the hybridization of these atomic orbitals. Chemical bonds are formed from the overlapping of atomic orbitals wherein the electrons are localized in the corresponding bond region.

The valence bond theory also goes on to explain the electronic structure of the molecules formed by this overlapping of atomic orbitals. It also emphasizes that the nucleus of one atom in a molecule is attracted to the electrons of the other atoms.

Postulates of Valence Bond Theory

The important postulates of the valence bond theory are listed below.

1. Covalent bonds are formed when two valence orbitals (half-filled) belonging to two different atoms overlap on each other. The electron density in the area between the two bonding atoms increases as a result of this overlapping, thereby increasing the stability of the resulting molecule.
2. The presence of many unpaired electrons in the valence shell of an atom enables it to form multiple bonds with other atoms. The paired electrons present in the valence shell do not take participate in the formation of chemical bonds as per the valence bond theory.
3. Covalent chemical bonds are directional and are also parallel to the region corresponding to the atomic orbitals that are overlapping.
4. Sigma bonds and pi bonds differ in the pattern that the atomic orbitals overlap in, i.e. pi bonds are formed from sidewise overlapping whereas the overlapping along the axis containing the nuclei of the two atoms leads to the formation of sigma bonds.

The formation of sigma and pi bonds is illustrated below.

It can be noted that sigma bonds involve the head-to-head overlapping of atomic orbitals whereas pi bonds involve parallel overlapping.

Number of Orbitals and Types of Hybridization

According to VBT theory the metal atom or ion under the influence of ligands can use its (n-1)d, ns, np, or ns, np, nd orbitals for hybridization to yield a set of equivalent orbitals of definite geometry such as octahedral, tetrahedral, square planar and so on. These hybrid orbitals are allowed to overlap with ligand orbitals that can donate electron pairs for bonding.

Applications of Valence Bond Theory

• The maximum overlap condition which is described by the valence bond theory can explain the formation of covalent bonds in several molecules.
• This is one of its most important applications. For example, the difference in the length and strength of the chemical bonds in H₂ and F₂ molecules can be explained by the difference in the overlapping orbitals in these molecules.
• The covalent bond in an HF molecule is formed from the overlap of the 1s orbital of the hydrogen atom and a 2p orbital belonging to the fluorine atom, which is explained by the valence bond theory.

Limitations of Valence Bond Theory

The shortcomings of the valence bond theory include

• Failure to explain the tetravalency exhibited by carbon.
• No insight is offered on the energies of the electrons.
• The theory assumes that electrons are localized in specific areas.
• It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordination compounds.
• No distinction between weak and strong ligands.
• No explanation for the colour exhibited by coordination compounds.

Also, Check ⇒ Crystal Field Theory

Solved Example

Question:

The spin only magnetic moment of [MnBr₄]^2- is 5.9BM. Predict the geometry of the complex ion.

Solution:

Since the coordination number of Mn2+ ion in the complex ion is 4. It will be either tetrahedral or square planar. But the fact that the magnetic moment of the complex ion is 5.9BM. It should be tetrahedral in shape rather than square planar because of the presence of five unpaired electrons in the d orbitals.

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