Valence shell electron pair repulsion theory (VSEPR)
The rules are based on the Points on a sphere model as it envisages the
arrangement of electron pairs as points on a spherical core. The rules have been
quite successful in predicting the shape of compounds whose central atom is a p
Ronald Gillespie block element and not very useful in the case of compounds of transition metals .
Mc Master Univ., Canada
The "AXE method" of electron counting
A represents the central atom and always has an implied subscript one.
X represents the number of ligands (atoms bonded to A).
E represents the number of lone pairs surrounding the central atom.
The electrons are arranged in pairs that are either bonding (shared) pairs [X] or
non bonding (unshared) pairs [E]. In the usual σ - π treatment this usually means
ignoring the π bonds temporarily since they will follow the σ bonds and therefore
the two bonding pairs of a double bond or three bonding pairs of a triple bond are
all primarily considered as a single point on the sphere.
e.g. H2O AX2E2 2 bonding pairs and 2 lone pairs on Oxygen as central atom
O=PCl3 AX4 4 bonding pairs π bond ignored with phosphorus as central atom
The rules
The pairs of electrons in the valence shell adopt that arrangement which
maximizes their distances apart. This in other words means that the bonding
and non bonding electron pairs are arranged as far apart from each other as
possible on the surface of a sphere with the atom A at the centre of the sphere.
Rules which take care of the deviations observed from the ideal geometry
Rule 1: A non bonding lone pair [E] occupies more space on the surface of the central
atom than a bonding pair [X]. In other words, lone pair- lone pair repulsion is greater
than lone pair- bond pair repulsion which is greater than bond pair-bond pair
repulsion. Lone pairs choose the largest site, e.g., equatorial in trigonal bipyramid and axial in pentagonal
bipyramid. If all sites are equal, lone pairs will be better placed trans to each other.
Rule 2: The strengths of the repulsions between bonds of different multiplicity
decreases in the order: triple–double > double– double > double–single >
single–single.
Rule 3: Bonding pairs to electronegative substituents occupy less space than
those to more electropositive substituents. Therefore angles between the single
bonds, decrease with increasing electronegativity of the substituent.
This decrease in domain size with increasing electronegativity of the substituent happens as more of the bonding
electron density is shifted to the electronegative substituent. In other words, the repulsion between single bonds
decreases with increasing electronegativity of the substituent and/or decreasing electronegativity of the central atom.
O O O
C C C N N
Cl F
H H Cl Cl F F Cl F
Cl F
116o 111o 108o 107o 102o
Shapes of compounds having odd number of electrons
The odd electron also has an influence on the molecular geometry similar to a
normal lone pair but of relatively lesser strength. As a result, the geometry
will be midway between the molecule with a full electron pair and the
molecule with one less electron pair on the central atom.
Nitrogen dioxide (NO2) (AX2E0.5) bent shape with an ONO angle 134°.
NO2− which is AX2E is also bent but has an ONO angle approximately of 120°
while NO2+ (AX2) is linear .
Similarly ClO2 (AX2E1.5) with a lone pair and an unpaired electron has OClO angle of 117.6°
while ClO2− with two lone pairs (AX2E2) has a OClO angle of 111°.
Exceptions to the VSEPR rules
1. Metal complexes and organometallic compounds based on transition elements
2. Many triatomic alkaline earth metal dihalides, although expected to be linear have
been found to be bent (approximate X-M-X angles: CaF2, 145°; SrF2, 120°; BaF2,
108°; SrCl2, 130°; BaCl2, 115°; BaBr2, 115° and BaI2, 105°). Gillespie has proposed that the
reason for the same is due to loss of spherical symmetry of the inner shell of the metal
atom due to polarising effect of the relatively electronegative halide substituent’s.
Li2O also is linear although it is expected to be bent and this has been ascribed to the
bonding being more ionic resulting in repulsion between the lithium atoms.
3. The silyl ether O(SiH3)2 has a relatively larger Si-O-Si angle (144.1°), while
similar bond angles of Cl2O (110.9°) and (CH3)2O (111.7°) are in the
expected range.
Gillespie's rationalization for this observation is that the localization of the lone
pairs, and therefore their ability to repel other electron pairs, is greatest when
the ligand has an electronegativity similar to or greater than, that of the central
atom. When the central atom is more electronegative, as in O(SiH3)2, the lone
pairs are less well-localised and have therefore a weaker repulsive effect.
4. Some molecules in which the central atom is from periods 3 and 4 and in which
the ligands are less electronegative, do not have sufficient space in their valence
shell to accommodate six bonding domains and a large lone pair domain. In such
molecules the lone pair is squeezed into a spherical domain surrounding the core
and inside the bonding domains (stereochemically inactive s orbital) which
therefore have an octahedral arrangement. Thus some AX6E molecule such as
SeCl62- and TeBr62- have a regular octahedral shape but with longer than normal
bonds.
Some new developments
The electron pair domain model
proposed by Gillespie and Harigittai in 1991 followed by Gillespie and Robinson in 1996.
This model was based not on pairs of electrons but on a region in space where there is
more probability of finding an electron pair (bonding or lone pair).
An electron pair domain is a region in space where there is an enhanced probability of
finding an electron pair.
An electron pair domain extends around the most probable position of finding an
electron pair as determined by the Pauli principle and the probability decreases on
increasing the distance from the most probable position.
A lone pair domain can in general be thought of as more spread out and larger than a
bonding pair domain as the electrons of a lone pair are subject to the attraction of only
one atomic nucleus while those of a bonding air are subject to the attraction of two
nuclei taking part in the bond formation.
A bonding pair domain therefore taken up less space around a nucleus compared to a
lone pair domain because the former is stretched out more towards the ligand/
substituent of the central atom. Why a lone pair occupies more space than a bonding
pair is well explained by the domain concept.
Ligand close packing model
The basis of this model is that the bond angles are determined by the
packing of the ligands or substituents around a central atom. Irrespective of
having lone pairs or not, the distance maintained between the substituents
on a central atom will be almost same while the bond lengths and bond
angles will be different as shown in the following examples.
Arrive at the shape of the following compounds using VSEPR theory
NSF3 IOF4− IO2F52− XeOF5− XeOF3-
Td Sq. Py PBP Pent Pyr [Link]
ICl2 +, ICl2− IF4+, IF4− XeF5+, XeF5−
bent Lin. See saw Sq. PL Sq. Pyr [Link]
IO3− IF52− [C6H4C(O)O] I(OAc)3 Kr2F3+
[Link] [Link] Sq. Pyr
Kr2F3+
Inorg. Chem., 2001, 40 (13), pp 3002–3017 Around central F : Td
Around Krypton : TBP
Arrangement Bonding Lone Occupancy/ Shape of the Examples
pairs pairs Steric number molecule
X E
Linear 2 0 2 Linear AX2 CO2, CS2, HCN, BeCl2, N2O, NO2+,
NCF, NCBr
Triangular 3 0 3 Triangular planar SO3, BF3, COCl2, NO3−, CO32−,
AX3 BO33-
2 1 3 Bent SO2, O3, NOCl, SnCl2, PbF2, NOF
(V shape) AX2E
Tetrahedral 4 0 4 Tetrahedral AX4 CH4, SiCl4, SO2Cl2, POCl3, XeO4,
NSF3, ClO4−. PO43-
3 1 4 Triangular NH3, PCl3, SOCl2, IO3−
Pyramidal AX3E
2 2 4 Bent AX2E2 H2O, SCl2, NSF, ICl2+, SeCl2,
[I(C6H5)2] + , Kr2F3+
Trigonal 5 0 5 Trigonal PF5, SF4O
bipyramid Bipyramidal AX5
4 1 5 See saw SF4, XeO2F2, IF4+, IOF3, IO2F2−
AX4E
3 2 5 Bent T shape ClF3, BrF3, XeOF2,
AX3E2 I(Ph)[(CF3C(O)O)]2
2 3 5 Linear XeF2, I3−, ICl2−, BrF2−. (C6F5)2Xe
AX2E3
Arrangement Bondi Lone Occupancy Shape of the Examples
ng pairs / molecule
pairs E Steric
X number
Octahedral 6 0 6 Octahedral SF6, PF6−, SiF62− ,AlF63− , IF6+
AX6
5 1 6 Square pyramidal BrF5, XeF5+ , IOF4−, TeF5− , SbF52−
AX5E [C6H4C(O)O] I(OAc)3
4 2 6 Square planar XeF4, IF4− , XeOF3−
AX4E2
Pentagonal 7 0 7 Pentagonal IF7, IO2F52−
bipyramid bipyramid IOF6-, TeF7-, CH3OTeF6-,
AX7 (CH3O)2TeF5- BiF72-, SbF72-
6 1 7 Pentagonal XeOF5−, IOF52− [IF5(C6H5)]−
Pyramid XeF6 ( monocapped octahedron)
AX6E
5 2 7 Pentagonal planar XeF5−, IF52−
AX5E2 X X
X X
Square 8 0 0 Square antiprism IF8-, XeF8, XeF8 2- (AX8E)
antiprism AX8 A
X
X
X
X
Platonic Solids
423 BC 347 BC
Archimedian Solids
