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자연과학대학
화학·나노과학전공
Journal papers
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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
남원우
;
이용민
;
서미숙
SCOPUS Author ID
남원우
Issue Date
2017
Journal Title
Nature Communications
ISSN
2041-1723
Citation
Nature Communications vol. 8
Publisher
Nature Publishing Group
Indexed
SCIE; 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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