Calculation of the geometries of binary transition metal carbonyl and dinitrogen complexes

Abstract

A simple molecular orbital method is used to calculate the minimum internal energy (MIE) structures of binary transition metal carbonyls and dinitrogen complexes. Agreement with the experimentally determined geometries of M(CO)_x(x= 2–6, M =d⁵ to d¹⁰ metal) is excellent. The change in energy of the predominantly metal d orbitals with geometry (Walsh diagrams) are shown to be metal–ligand overlap integral determined and the calculated MIE geometries are readily rationalised by Jahn–Teller considerations and the use of the Walsh diagrams.