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The Directionality of d‐Orbitals and Molecular‐Mechanics Calculations of Octahedral Transition‐Metal Compounds
Author(s) -
Comba Peter,
Ströhle Marc,
Hambley Trevor W.
Publication year - 1995
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19950780812
Subject(s) - chemistry , force field (fiction) , atomic orbital , octahedron , transition metal , force constant , molecular mechanics , field (mathematics) , computational chemistry , molecular orbital , metal , molecular dynamics , molecular physics , crystallography , molecule , quantum mechanics , physics , crystal structure , biochemistry , mathematics , organic chemistry , pure mathematics , catalysis , electron
A novel approach to modeling the angular geometry about the metal centre in transition‐metal complexes, using a variation of classical molecular‐mechanics calculations, is presented. The approach is based on the combination of 1,3‐nonbonded interactions around the metal centre and a harmonic sine function with a ligandfield‐dependent force constant for the L–M–L′ terms. Force‐field parameters for four‐, five‐, and six‐coordinated first‐row transition‐metal coordination centres and a variety of ligands containing N‐, S‐, and O‐donor sets are given. The new ‘electronically doped’ force field is shown to generally lead to computed structures with higher accuracy than those obtained when the coordination geometries are modeled with 1,3‐nonbonded interactions alone.