Our understanding of the mechanisms for the insertion reactions of molecular oxygen into metal-hydride bonds has grown significantly in recent years. Several different mechanisms have been established for the aerobic oxidation of Pd(II), Pt(IV), Rh(III),<sup>, </sup>Ir(III), and Au(I) hydride complexes. Here, we report the synthesis of a thermally stable Au(III) hydride and present its reactivity with molecular oxygen to form a Au(III) hydroperoxide, the first directly observed oxygen insertion reaction for a Au(III) hydride. Kinetic and mechanistic studies of the aerobic oxidation will be discussed and compared to other M-H oxygen insertion reactions, along with reactivity studies of the Au(III)-OOH and the related Au(III)-OH complex.

Synthesis and aerobic oxidation of a gold(III) hydride

ACS Spring 2022

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