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In Modern day Chemistry, Bent's rule play a vital role in shape determination of molecules especially having TBP geometry.
Bent's rule describes and explains the relationship between theoretical hybridization of central atoms in molecules and the electronegativities of substituents.
The rule was stated by Henry Bent as follows: "Atomic character concentrates in orbitals directed toward electropositive substituents".
The chemical structure of molecules intimately related to its properties and reactivity. Valence bond theory proposes that molecular structures are due to covalent bonds between the atoms and that each bond consists of two overlapping and typically hybridized atomic orbitals. Traditionally, p-block elements in molecules are assumed to hybridized strictly as spn, where n is either 1, 2, or 3. In addition, the hybrid orbitals are all assumed to be equivalent (i.e. the n+1 spn orbitals have the same p character). Results from this approach are usually good, but they can be improved upon by allowing hybridised orbitals with noninteger and unequal p character. Bent's rule provides a qualitative estimate as to how these hybridized orbitals should be constructed. Bent's rule is that in a molecule, a central atom bonded to multiple groups will hybridize so that orbitals with more s character are directed towards electropositive groups, while orbitals with more p character will be directed towards groups that are more electronegative. By removing the assumption that all hybrid orbitals are equivalent spn orbitals, better predictions and explanations of properties such as molecular geometry and bond strength can be obtained.
Bent's rule can be generalized to d-block elements as well. The hybridisation of a metal center is arranged so that orbitals with more s character are directed towards ligands that form bonds with more covalent character. Equivalently, orbitals with more d character are directed towards groups that form bonds of greater ionic character.
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In chemistry, Bent's rule describes and explains the relationship between the orbital hybridization of central atoms in molecules and the electronegativities of substituents. The rule was stated by Henry Bent as follows:
Atomic character concentrates in orbitals directed toward electropositive substituents.
The chemical structure of a molecule is intimately related to its properties and reactivity. Valence bond theory proposes that molecular structures are due to covalent bonds between the atoms and that each bond consists of two overlapping and typically hybridised atomic orbitals. Traditionally, p-block elements in molecules are assumed to hybridise strictly as spn, where n is either 1, 2, or 3. In addition, the hybrid orbitals are all assumed to be equivalent (i.e. the n + 1 spn orbitals have the same p character). Results from this approach are usually good, but they can be improved upon by allowing isovalent hybridization, in which the hybridised orbitals may have noninteger and unequal p character. Bent's rule provides a qualitative estimate as to how these hybridised orbitals should be constructed. Bent's rule is that in a molecule, a central atom bonded to multiple groups will hybridise so that orbitals with more s character are directed towards electropositive groups, while orbitals with more p character will be directed towards groups that are more electronegative. By removing the assumption that all hybrid orbitals are equivalent spn orbitals, better predictions and explanations of properties such as molecular geometry and bond strength can be obtained. Bent's rule has been proposed as an alternative to VSEPR theory as an elementary explanation for observed molecular geometries of simple molecules with the advantages of being more easily reconcilable with modern theories of bonding and having stronger experimental support.
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