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

Chemical Science
Tzung-Wen ChiouWen-Feng Liaw

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 [NiIII(κ1-OCO˙-)(P(C6H3-3-SiMe3-2-S)3)]- complex. The formation of this unusual NiIII(κ1-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 t...Continue Reading

References

Oct 1, 1996·Chemical Reviews·Dorothy H. Gibson
Sep 18, 2004·Science·Ingrid Castro-RodriguezKarsten Meyer
Aug 11, 2005·Journal of the American Chemical Society·Ingrid Castro-Rodriguez, Karsten Meyer
Jan 4, 2007·Journal of the American Chemical Society·Connie C LuJonas C Peters
Jun 15, 2007·Chemical Reviews·Toshiyasu SakakuraHiroyuki Yasuda
Jul 12, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Michele Aresta, Angela Dibenedetto
Feb 21, 2008·Inorganic Chemistry·Benjamin C FullmerKenneth G Caulton
Apr 16, 2008·Journal of the American Chemical Society·Matthew T Whited, Robert H Grubbs
Aug 22, 2008·Journal of the American Chemical Society·Suzanne C BartKarsten Meyer
Jan 8, 2009·Journal of the American Chemical Society·Anukul JanaDietmar Stalke
Jan 16, 2010·Science·Raja AngamuthuElisabeth Bouwman
Dec 13, 2012·Chemical Society Reviews·Cyrille CostentinJean-Michel Savéant
Jun 3, 2014·Journal of Agricultural and Food Chemistry·Nurul A M AzmanMaria Pilar Almajano
Jul 30, 2014·Chemical Communications : Chem Comm·Yeong-Eun KimYunho Lee
Sep 11, 2014·Angewandte Chemie·Johannes G RebeleinMarkus W Ribbe
Mar 24, 2015·Journal of the American Chemical Society·Yeong-Eun KimYunho Lee
May 1, 2015·Angewandte Chemie·Jochen FesselerHolger Dobbek
Jul 24, 2015·Journal of the American Chemical Society·Guanghua JinSébastien Bontemps

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