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

Bin Wang, Yong Min Lee, Woon Young Tcho, Samat Tussupbayev, Seoung Tae Kim, Yujeong Kim, Mi Sook Seo, Kyung Bin Cho, Yavuz Dede, Brenna C. Keegan, Takashi Ogura, Sun Hee Kim, Takehiro Ohta, Mu Hyun Baik, Kallol Ray, Jason Shearer, Wonwoo Nam

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Abstract

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)(CF3 SO3)]+ (1) in the presence of [Ru II (bpy)3]2+, Na2 S2 O8, 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 Co IV-O species in cobalt-catalysed oxidation of organic substrates as well as in the catalytic oxidation of water that evolves molecular oxygen.

Original languageEnglish
Article number14839
JournalNature Communications
Volume8
DOIs
StatePublished - 24 Mar 2017

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