Stoichiometric oxidations of σ-bonds:: Radical and possible non-radical pathways

Many transition metal complexes accomplish or catalyze the oxidation of C-H, O-H, and other sigma-bonds. Under aerobic conditions, metal complexes typically modulate an autoxidation radical chain. In anaerobic reactions, a metal complex can be the reactive species that attacks the sigma-bond, in many cases by abstracting a hydrogen atom from the substrate. Examples described here include the oxidation of alkylaromatic compounds by ruthenium oxo complexes and reactions of deprotonated iron(III) complexes. In general, these reactions occur with addition of H(+) to a ligand and e(-) to the metal center. Rate constants for such hydrogen-atom transfer reactions can, in many cases, be predicted by the Marcus cross relation. Autoxidation and metal-mediated radical mechanisms are so prevalent that proposals of non-radical oxidations of C-H bonds carry a higher burden of proof. It is argued here that the oxidation of H(2) by OsO(4) occurs by a non-radical, [3 + 2] mechanism. OsO(4) oxidizes alkanes under similar aqueous conditions. For example, isobutane is oxidized to tert-butanol, and cyclohexane to adipate and succinate. The alkane oxidations do not have the hallmarks of a radical mechanism but sufficient questions remain that a radical pathway cannot be excluded at this time. (c) 2006 Elsevier B.V. All rights reserved.