Highly covalent metal–ligand π bonding in chelated bis- and tris(iminoxolene) complexes of osmium and ruthenium
Jacqueline Gianino, Seth N. Brown
Abstract
) on aerobic reaction with divalent metal precursors. The complexes' structural and electronic features are well described using a simple bonding model that emphasizes the covalency of the π bonding between the metal and iminoxolene ligands rather than attempting to dissect the parts into discrete oxidation states. Emphasizing the continuity of bonding between disparate complexes, the structural data from a variety of Os and Ru complexes show good correlations to π bond order, and the response of the intraligand bond distances to the bond order can be analyzed to illuminate the polarity of the bonding between metal and the redox-active orbital on the iminoxolenes. The osmium compounds'π bonding orbitals are about 40% metal-centered and 60% ligand-centered, with the ruthenium compounds' orbitals about 65% metal-centered and 35% ligand-centered.