Bent's rule

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Bents rule was formulated in 1961 by American chemist Henry Bent to explain deviations in
structures predicted from the orbital hybridisation theory.[1] 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.[2] 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.[3] 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.[4] 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.

Bents rule was derived from the comparison of experimentally determined physical properties
of molecules, correlated with valence bond structures and bond hybridization.[5] 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.

Contents [hide]

1 Examples

2 Exceptions

3 See also

4 ReferencesAccording 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).[5] 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).[6]

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

electropositive substituents.[1] However, this general statement is only true for main group
elements.[1] For the main group elements, atomic p-orbitals are directed towards more
electronegative substituents.[5] 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.[7] Also, electron density can be more easily withdrawn (by
electronegative substituents) from higher lying p-orbitals than from s-orbitals.[5]

Transition metal complexes are the exception to Bents rule. It has been experimentally
determined[5] 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.[5] Transition metal bonds are essentially sdx hybridized, with very little
contribution from the p-orbitals.[5]

A generalized form of Bents rule can be stated as follows: The energetically lower lying valence
orbital concentrates in bonds directed toward electropositive substituents.[5] This satisfies both
main group and transition metal complexes.

[edit]See also
Structure of Me2XCl2

[edit]Exceptions