Paramagnetic Resonance Studies of Bonding in Vanadyl and Molybdenyl Metal Complexes

Abstract

Electron spin resonance data for [VOCl5]3— and [MoOCl5]2— in dilute single crystals are reported and and analyzed to give the spin Hamiltonian parameters for these complexes. A molecular orbital formulation is given for the spin Hamiltonian parameters, and terms dependent on spin—orbit interactions near ligand nuclei are found. This formulation is applied to the experimental results by means of an empirical method including radial expansion effects, and estimates of certain LACO—MO coefficients are obtained. The bonding in [VOCl5]3—, [VO(H2O)5]2+, and [MlOCl5]2— is discussed in terms of these LCAO—MO coefficients.