Molecular orbital theory of organometallic compounds. Part XII. Nature of metal–metal bonding in some binuclear metal carbonyls

Abstract

The nature of the metal–metal bond in a series of binuclear metal carbonyls M₂(CO)₁₀(M₂= Mn₂, Tc₂, Re₂, and MnRe) is described by application of the self-consistent charge and configuration (SCCC) molecular orbital method. Good correlation between calculated quantities such as orbital energies and overlap populations and experimental quantities such as photoionization spectra and bond dissociation energies are obtained. It is suggested that the term ‘unsupported’ metal–metal bond, especially for atoms of the first transition series requires modification because of the important contribution to the metal–metal bond energy of the cross-interaction between a metal atom and ligands directly bonded to the other metal atom.