Bent's rule

Bents rule was formulated in 1961 by American chemist Henry Bent to explain deviations in structures
predicted from the orbital hybridisation theory. The rule states: atomic s character tends to concentrate

in orbitals that are directed toward electropositive groups and atomic p character tends to concentrate
in orbitals that are directed toward electronegative groups . This rule, which is experimentally
observed and supported by molecular orbital calculations, is a useful tool in inorganic and organic
chemistry. Bent based his rule on the perturbation theory, and suggested that isovalent orbital
hybridization should transfer more s character to the more electropositive-bonding orbital to maximize
bonding energy. Hybrid orbitals for main group elements consist of one s and three p orbitals, with the
s orbital having lower energy. To have more s character means that the bonding orbital is lower in
energy and shaped more like an s orbital rather than a p orbital. In other words, ligand orbitals tend to
be rich in p character because of higher electronegativity, with s character concentrated on the central
metal. However, in cases where the metal has a lone pair, the lone pair orbital is high in s character.
This is because s orbitals are closer to the nucleus, allowing for greater stabilization of the lone pair.

When there is more 2p character in the N-F bonds there is better overlap, (overlap integral
(N2p)(F 2p) d) and this of course results in a lower energy situation.
More electronegative substituents prefer site which has higher p character or in other words less s
character.

Bents rule was derived from the comparison of experimentally determined physical properties of
molecules, correlated with valence bond structures and bond hybridization. This rule has been used to
qualitatively describe molecular geometries and predict the structure of substituted atoms or molecules.
While Bents rule was originally intended to describe bonding in elements of the first row of the
periodic table, it also experimentally holds true for transition metal complexes.

Examples
According to Bents rule, molecular geometry can be explained and predicted by changing
the substituent group. In the molecule Me2XCl2 (where X=main group elements C, Si, Ge, Sn, Pb), the
bond

angle

ClXCl

is

smaller

than

the

CXC

bond

angle.

With

the

highly electronegative halogen substituent, Cl, more p character is concentrated on central atom in X
Cl than XC bonds. Subsequently, bonds with greater p character have smaller bond angles than those
with greater s character. For example, when X=C, the ClCCl has 108.3 bond angle that is smaller
than CCC bond angle, 113.0. In addition, this can be applied to heavier main group elements. When
X=Si, ClSiCl has a bond angle (107.2) that is smaller than that of CSiC (114.7). In another
example, Cl can be substituted to form the molecule (CH3)2PbF2. This molecule is distorted following
Bent's rule, in which the bond angle of CPbC (134.8) is larger than the angle of the FPbF bond
(101.4).

Exceptions

Bond angles of Me2TiCl2. The ClTiCl bond angles suggest a deviation from Bent's rule.

According to Bents rule, Atomic s character concentrates in orbitals directed towards electropositive

substituents. However, this general statement is only true for main group elements. For the main group
elements, atomic p-orbitals are directed towards more electronegative substituents. This can be
rationalized by the fact that the decreased angles of bonds with more p character coincide with the
decreased steric demands of more electronegative atoms. Also, electron density can be more easily
withdrawn (by electronegative substituents) from higher lying p-orbitals than from s-orbitals.
Transition metal complexes are the exception to Bents rule. It has been experimentally determined that
the group 4 transition metal compounds of Ti-Hf do not rigorously follow Bents rule. With these
complexes, the more electronegative substituents have larger bond angles (indicating greater s
character), which goes against Bents rule. This can be explained by the fact that with transition metals,
the energy levels of the d-orbitals are generally below the energy of the s-orbitals, thus the more
electronegative substituents will be attracted to the higher lying s-orbitals. Transition metal bonds are
essentially sdx hybridized, with very little contribution from the p-orbitals.
A generalized form of Bents rule can be stated as follows: The energetically lower lying valence orbital

concentrates in bonds directed toward electropositive substituents. This satisfies both main group and
transition metal complexes.