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Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex.

Bin WangYong-Min LeeWoon-Young TchoSamat TussupbayevSeoung-Tae KimYujeong KimMi Sook SeoKyung-Bin ChoYavuz DedeBrenna C KeeganTakashi OguraSun Hee KimTakehiro OhtaMu-Hyun BaikKallol RayJason ShearerWonwoo Nam
Published in: Nature communications (2017)
Terminal cobalt(IV)-oxo (CoIV-O) species have been implicated as key intermediates in various cobalt-mediated oxidation reactions. Herein we report the photocatalytic generation of a mononuclear non-haem [(13-TMC)CoIV(O)]2+ (2) by irradiating [CoII(13-TMC)(CF3SO3)]+ (1) in the presence of [RuII(bpy)3]2+, Na2S2O8, and water as an oxygen source. The intermediate 2 was also obtained by reacting 1 with an artificial oxidant (that is, iodosylbenzene) and characterized by various spectroscopic techniques. In particular, the resonance Raman spectrum of 2 reveals a diatomic Co-O vibration band at 770 cm-1, which provides the conclusive evidence for the presence of a terminal Co-O bond. In reactivity studies, 2 was shown to be a competent oxidant in an intermetal oxygen atom transfer, C-H bond activation and olefin epoxidation reactions. The present results lend strong credence to the intermediacy of CoIV-O species in cobalt-catalysed oxidation of organic substrates as well as in the catalytic oxidation of water that evolves molecular oxygen.
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