Insertion of Molecular Oxygen into a Gold(III)-Hydride Bond.

The use of molecular oxygen as an oxidant in chemical synthesis has significant environmental and economic benefits, and it is widely used as such in large-scale industrial processes. However, its adoption in highly selective homogeneous catalytic transformations, particularly to produce oxygenated organics, has been hindered by our limited understanding of the mechanisms by which O 2 reacts with transition metals. Of particular relevance are the mechanisms of the reactions of oxygen with late transition metal hydrides as these metal centers are better poised to release oxygenated products. Homogeneous catalysis with gold complexes has markedly increased, and herein we report the synthesis and full characterization of a rare Au III -H, supported by a diphosphine pincer ligand ( t Bu PCP = 2,6-bis(di- tert -butylphosphinomethyl)benzene). [( t Bu PCP)Au III -H] + was found to cleanly react with molecular oxygen to yield a stable Au III -OOH complex that was also fully characterized. Extensive kinetic studies on the reaction via variable temperature NMR spectroscopy have been completed, and the results are consistent with an autoaccelerating radical chain mechanism. The observed kinetic behavior exhibits similarities to that of previously reported Pd II -H and Pt IV -H reactions with O 2 but is not fully consistent with any known O 2 insertion mechanism. As such, this study contributes to the nascent fundamental understanding of the mechanisms of aerobic oxidation of late metal hydrides.