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

Title
Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex
Authors
Wang B.Lee Y.-M.Tcho W.-Y.Tussupbayev S.Kim S.-T.Kim Y.Seo M.S.Cho K.-B.Dede Y.Keegan B.C.Ogura T.Kim S.H.Ohta T.Baik M.-H.Ray K.Shearer J.Nam W.
Ewha Authors
남원우이용민서미숙
SCOPUS Author ID
남원우scopus
Issue Date
2017
Journal Title
Nature Communications
ISSN
2041-1723JCR Link
Citation
Nature Communications vol. 8
Publisher
Nature Publishing Group
Indexed
SCI; SCIE; SCOPUS WOS scopus
Document Type
Article
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. © The Author(s) 2017.
DOI
10.1038/ncomms14839
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자연과학대학 > 화학·나노과학전공 > Journal papers
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