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Issue 6, 2016
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[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex

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Abstract

Carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO2, i.e. insertion of CO2 producing bicarbonate/acetate/formate, cleavage of CO2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO2 affording CO/HCOOH/CH3OH/CH4/C2H4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO2 by the [NiIII(OMe)(P(C6H3-3-SiMe3-2-S)3)] complex, yielding the [NiIII1-OCO˙)(P(C6H3-3-SiMe3-2-S)3)] complex. The formation of this unusual NiIII1-OCO˙) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [NiIII(SPh)], [NiII(CO)], and [NiII(N2H4)] toward CO2, in contrast, demonstrates that the ionic [NiIII(OMe)] core attracts the binding of weak σ-donor CO2 and triggers the subsequent reduction of CO2 by the nucleophilic [OMe] in the immediate vicinity. This metal–ligand cooperative activation of CO2 may open a novel pathway promoting the subsequent incorporation of CO2 in the buildup of functionalized products.

Graphical abstract: [NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex

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Publication details

The article was received on 03 Dec 2015, accepted on 16 Feb 2016 and first published on 24 Feb 2016


Article type: Edge Article
DOI: 10.1039/C5SC04652A
Citation: Chem. Sci., 2016,7, 3640-3644
  • Open access: Creative Commons BY license
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    [NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex

    T. Chiou, Y. Tseng, T. Lu, T. Weng, D. Sokaras, W. Ho, T. Kuo, L. Jang, J. Lee and W. Liaw, Chem. Sci., 2016, 7, 3640
    DOI: 10.1039/C5SC04652A

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