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O 2 Activation by a Heterobimetallic Zr/Co Complex

2019; American Chemical Society; Volume: 141; Issue: 24 Linguagem: Inglês

10.1021/jacs.9b04215

1943-2984

Hongtu Zhang, Gillian P. Hatzis, Curtis E. Moore, Diane A. Dickie, Mark W. Bezpalko, Bruce M. Foxman, Christine M. Thomas,

Metal-Catalyzed Oxygenation Mechanisms

Oxygen reduction is a critical half reaction in renewable fuel cell development and a key step in the development of aerobic oxidation reactions. Herein, we report rapid two-electron O2 reduction by a d0 ZrIV center with an appended redox-active Co–I site serving as an electron reservoir. The early/late heterobimetallic Zr/Co complex (THF)Zr(MesNPiPr2)3CoCNtBu (1) reacts readily with O2 and O atom transfer reagents to generate reactive oxygenated species including terminal peroxo and oxo complexes, (O2)Zr(MesNPiPr2)3CoCNtBu (2) and O≡Zr(MesNPiPr2)3CoCNtBu (3). The bimetallic Zr/Co complex provides a new cooperative synthetic pathway to promote multielectron redox processes such as oxygen reduction, with each metal playing a distinct role as a substrate binding site or redox mediator.