Dioxygen Activation by Internally Aromatic Metallacycle: Crystallographic Structure and Mechanistic Investigations.

ABSTRACT: Mononuclear metal-peroxo species are invoked as the key intermediates in metalloenzymatic or synthetic catalysis. However, either transience or sluggishness reactivity of synthetic analogs of metal-peroxo species impedes our understanding of oxygen activation mechanism. Herein, we designed and characterized a dioxygen-derived mononuclear osmium-peroxo complex, in which the peroxo ligand is stabilized by internally aromatic metallacycle. We demonstrate that the osmium-peroxo species shows catalytic activity toward promoterless alcohol dehydrogenations. Furthermore, computational studies provide a new mechanism for the osmium-peroxo-mediated alcohol oxidation, starting with the concerted double-hydrogen transfer and followed by the generation of osmium-oxo species. Interestingly, the interna

SUBMITTER: Deng Z 

PROVIDER: S-EPMC7399181 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature