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

doi:10.1038/ncomms14839

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

146 Scopus citations

Abstract

Terminal cobalt(IV)-oxo (Co^IV-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)Co^IV (O)]²⁺ (2) by irradiating [Co^II (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 language	English
Article number	14839
Journal	Nature Communications
Volume	8
DOIs	https://doi.org/10.1038/ncomms14839
State	Published - 24 Mar 2017

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@article{51aa82f28259489794281ca203e90d2d,

title = "Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex",

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.",

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

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doi = "10.1038/ncomms14839",

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T1 - Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex

AU - Wang, Bin

AU - Lee, Yong Min

AU - Tcho, Woon Young

AU - Tussupbayev, Samat

AU - Kim, Seoung Tae

AU - Kim, Yujeong

AU - Seo, Mi Sook

AU - Cho, Kyung Bin

AU - Dede, Yavuz

AU - Keegan, Brenna C.

AU - Ogura, Takashi

AU - Kim, Sun Hee

AU - Ohta, Takehiro

AU - Baik, Mu Hyun

AU - Ray, Kallol

AU - Shearer, Jason

AU - Nam, Wonwoo

PY - 2017/3/24

Y1 - 2017/3/24

N2 - 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.

AB - 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.

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

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