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

Here, 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.
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [1] ;  [4] ;  [5] ;  [5] ;  [1]
  1. National Tsing Hua Univ., Hsinchu (Taiwan)
  2. Chung Yuan Christian Univ., Taoyuan (Taiwan)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. National Taiwan Normal Univ., Taipei (Taiwan)
  5. National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
Publication Date:
OSTI Identifier:
1251399
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 1021; Journal Issue: C; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY