The Directionality of d‐Orbitals and Molecular‐Mechanics Calculations of Octahedral Transition‐Metal Compounds

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Abstract
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.