VSEPR

The ideal electronic symmetry of a molecule consisting of a central atom surrounded by a number of substituents (bonded atoms and non-bonding electrons) is characteristic of the total number of substituents, and is determined solely by geometric considerations - the substituents are arranged so as to maximize the distances amongst them.

THE BASIC ASSUMPTIONS OF THIS THEORY ARE SUMMARIZED BELOW

The electron pair s in the valence shell around the central atom of a molecule repel each other and tend to orient in space so as to minimize the repulsions and maximize the distance between them . There are two types of valence shell electron pa irs viz., i) Bond pair s and ii) Lone pair s Bond pair s are shared by two atoms and are attracted by two nuclei. Hence they occupy less space and cause less repulsion. Lone pairs are not involved in bond formation and are in attraction with only one nucleus. Hence they occupy more space. As a result, the lone pair s cause more repulsion . The order of repulsion between dif ferent types of electron pairs is as follows: Lone pair - Lone pair > Lone Pair - Bond pair > Bond pair Bond pair In VSEPR theor y, the multiple bonds are treated as if they were single bonds. The electron pair s in multiple bonds are treated collectively as a single super pair.

 The repulsion caused by bonds increases with increase in the number of bonded pairs between two atoms i.e., a triple bond causes more repulsion than a double bond which in turn causes more repulsion than a single bond. The shape of a molecule can be predicted from the number and type of valence shell electron pairs around the central atom. When the valence shell of central atom contains only bond pairs, the molecule assumes symmetrical geometry due to even repulsions between them. However the symmetry is distorted when there are also lone pairs along with bond pairs due to uneven repulsion forces.

Primary & Secondary effects on bond angle and shape:

The bond angle decreases due to the presence of lone pairs, which cause more

repulsion on the bond pairs and as a result the bond pairs tend to come closer. The repulsion between electron pairs increases with increase in electronegativity of central atom and hence the bond angle increases. The bond pairs are closer and thus by shortening the distance between them, which in turn increases the repulsion. Hence the bonds tend to move away from each other. However the bond angle decreases when the electronegativities of ligand atoms are more than that of central atom. There is increase in the distance between bond pairs since they are now closer to ligand atoms. Due to this, they tend to move closer resulting in the decrease in bond angle. The bond angle decreases with increase in the size of central atom. However the bond angle increases with increase in the size of ligand atoms, which surround the central atom. The bond angles are also changed when multiple bonds are present. It is due to uneven repulsions.

RELATION BETWEEN NUMBER & TYPE OF VALENCE ELECTRON PAIRS WITH THE SHAPE OF MOLECULE
The shape of molecule and also the approximate bond angles can be predicted from the number and type of electron pairs in the valence shell of central atom as tabulated below.

Steric Number
The steric number of a molecule is the number of atoms bonded to the central atom of a molecule plus the number of lone pairs on the central atom. It is often used in VSEPR theory(valence shell electron-pair repulsion theory) in order to determine the particular shape, ormolecular geometry, that will be formed.

STEPS INVOLVED IN PREDICTING THE SHAPES OF MOLECULES USING VSEPR THEORY

The

first step in determination of shape of a molecule is to write the Lewis dot structure of the molecule. Then find out the number of bond pairs and lone pairs in the valence shell of central atom. While counting the number of bond pairs, treat multiple bonds as if they were single bonds. Thus electron pairs in multiple bonds are to be treated collectively as a single super pair.

Steric No.

No. of No. of lone bonding pair electrons groups (pair on 'central' electrons) on atom 'central' atom 0 0 1 0 1 2 2 3 2 4 3 2

Electron-pair Geometry (Structure)

linear trigonal planar trigonal planar tetrahedral tetrahedral tetrahedral

Molecular Geometry (Shape)

linear trigonal planar bent tetrahedral trigonal pyramidal bent

Bond Angle

2 3 3 4 4 4

180 120 less than 120 109.5 less than 109.5 less than 109.5

Steric No.

No. of lone No. of pair bonding electrons groups (pair on 'central' electrons) on atom 'central' atom 0 5

Electronpair Geometry trigonal bipyramidal Steric No.

Molecular Geometry
trigonal bipyramidal No. of lone pair electrons on 'central' atom

Bond Angle

90, 120 and 180 No. of bonding groups (pair electrons) on 'central' atom

5
5 6 6 6

2
3 0 1 2

3
2 6 5 4

trigonal bipyramidal
trigonal bipyramidal octahedral octahedral octahedral

T-shaped
linear octrahedral square pyramidal square planar

90 and 180
180 90 and 180 90 and 180 90 and 180

Even though the VSEPR model is useful to predict the shapes of molecules, it fails to predict the shapes of isoelectronic species and transition metal compounds. This model does not take relative sizes of substituents and stereochemically inactive lone pairs into account. As a result, VSEPR is not appropriate to apply to heavy d-block species that experience the stereochemical inert pair effect.

Shapes
Linear

Trigonal planar
Angular Tetrahedral

Trigonal pyramidal

Angular Trigonal

bipyramidal

See

saw or distorted tetrahedral

 T-Shape

Linear

Octahedral

Square pyramidal

 Square planar

Pentagonal bipyramidal

Pentagonal pyramidal