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Reduction of CO2 by Hydrosilanes in the Presence of Formamidinates of Group 13 and 12 Elements

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    Reduction of CO2 by Hydrosilanes in the Presence of Formamidinates of Group 13 and 12 Elements
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    • Weiheng Huang
      Weiheng Huang
      Organometallics: Materials and Catalysis laboratories, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35700 Rennes, France
      More by Weiheng Huang
    • Thierry Roisnel
      Thierry Roisnel
      Centre de diffraction X, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35700 Rennes, France
      More by Thierry Roisnel
    • Vincent Dorcet
      Vincent Dorcet
      Centre de diffraction X, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35700 Rennes, France
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    • Clement Orione
      Clement Orione
      CRMPO, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35700 Rennes, France
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    • Evgueni Kirillov*
      Evgueni Kirillov
      Organometallics: Materials and Catalysis laboratories, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35700 Rennes, France
      *E-mail for E.K.: [email protected]
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      Orcidhttp://orcid.org/0000-0002-5067-480X
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    Organometallics

    Cite this: Organometallics 2020, 39, 5, 698–710
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    https://doi.org/10.1021/acs.organomet.9b00853
    Published February 24, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Homoleptic complexes 1-M of group 13 and 12 elements (M = B–In and M = Zn, respectively) incorporating electron-withdrawing formamidinate ligands {(C6F5)N═CHN(C6F5)}− ({NCN}−) were synthesized and isolated in high yields. The compounds were characterized by X-ray crystallography, NMR spectroscopy, and elemental analysis. While the single-component 1-M appeared to be sluggishly active or inactive in the reduction of CO2 with hydrosilanes, a good catalytic performance was achieved with the two-component systems derived from combinations of 1-M and E(C6F5)3 (E = B, Al). In particular, the binary combination 1-Al/B(C6F5)3 showed the best performance within the whole series, thus providing quantitative hydrosilane (Et3SiH) conversions under a range of conditions (PCO2, temperature, benzene or bromobenzene solvent) and affording mainly CH2(OSiEt3)2 and CH4 as products. Kinetic and mechanistic studies revealed that at the initiation step the binary catalytic systems undergo a complex transformation in the presence of CO2/Et3SiH, affording the products of 1-Al decomposition: namely, (C6F5)N(H)SiEt3, (C6F5)N(Me)SiEt3, {NCN}SiEt3, and also some unidentified aluminum species. Thus, the overall process of the reduction of CO2 with hydrosilanes is presumed to be catalyzed by complex multisite systems, evolved from the formamidinate precursor 1-Al, implicating different tandem combinations of N-base/B(C6F5)3 with putative Al-containing species.

    Copyright © 2020 American Chemical Society

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    • Selected catalytic results, NMR data, and kinetic plots (PDF)

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    CCDC 1950208–1950214 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

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    Organometallics

    Cite this: Organometallics 2020, 39, 5, 698–710
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.9b00853
    Published February 24, 2020
    Copyright © 2020 American Chemical Society
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