Molecular orbital theory of organometallic compounds. Part XIII. Electronic structures and reactivities of halogenopentacarbonyl compounds of manganese and rhenium

Abstract

The electronic structures of halogenopentacarbonyl-manganese and -rhenium are discussed by application of the self-consistent charge and configuration molecular orbital (SCCC–MO) method. Good correlation between calculated quantities such as orbital energies and overlap populations and experimental quantities such as photoionization spectra and vibrational force constants are obtained. The relative reactivities of this series to carbonylsubstitution which proceeds by a dissociative mechanism is also found to correlate with M–C overlap populations in a satisfactory manner.