Molecular orbital theory of organometallic compounds. Part X. Electronic structures of the hexacarbonylmetals of Group VI

Abstract

A molecular orbital study employing the Self-Consistent Charge Method (SCCC) for the hexacarbonyls of chromium, molybdenum, and tungsten is reported. Good correlation of observed photoelectron spectra and bond energies with calculated energy levels is found. Correlation of force constants (e.g., F_M–C) is made with the total(σ+π) overlap population emphasizing that comparison of frequencies between carbonyl compounds of different metals is only valid if allowance is made for variation in both σ and π bonding. A discussion of solvent effects in the i.r. spectrum is also given.