Selective catalytic frustrated Lewis pair hydrogenation of CO2 in the presence of silylhalides

Tongtong Wang; Maotong Xu; Andrew R. Jupp; Zheng‐Wang Qu; Stefan Grimme; Douglas W. Stephan

doi:10.1002/anie.202112233

Selective catalytic frustrated Lewis pair hydrogenation of CO₂ in the presence of silylhalides

Tongtong Wang, Maotong Xu, Andrew R. Jupp, Zheng‐Wang Qu, Stefan Grimme, Douglas W. Stephan

Chemistry

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Abstract

The frustrated Lewis pair (FLP) derived from 2,6-lutidine and B(C₆F₅)₃ is shown to mediate the catalytic hydrogenation of CO₂ using H₂ as the reductant and a silylhalide as an oxophile. The nature of the products can be controlled with the judicious selection of the silylhalide and the solvent. In this fashion, this metal-free catalysis affords avenues to the selective formation of the disilylacetal (R₃SiOCH₂OSiR₃), methoxysilane (R₃SiOCH₃), methyliodide (CH₃I) and methane (CH₄) under mild conditions. DFT studies illuminate the complexities of the mechanism and account for the observed selectivity.

Original language	English
Pages (from-to)	25771-25775
Journal	Angewandte Chemie International Edition
Volume	60
Issue number	49
Early online date	4 Oct 2021
DOIs	https://doi.org/10.1002/anie.202112233
Publication status	E-pub ahead of print - 4 Oct 2021

Bibliographical note

Funding Information:
D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Canada Council for the Arts and the RSC(UK) are thanked for a 2020 Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (Leibniz prize to S.G) for financial support. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. A.R.J. is grateful for the award of a Banting Fellowship for funding. Open Access funding enabled and organized by Projekt DEAL.

Keywords

CO hydrogenation catalysis
acetal
frustrated Lewis pair
methane
methyliodide

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.202112233Licence: Creative Commons: Attribution (CC BY)

WangT2021Selective Final published version, 1.15 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

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title = "Selective catalytic frustrated Lewis pair hydrogenation of CO2 in the presence of silylhalides",

abstract = "The frustrated Lewis pair (FLP) derived from 2,6-lutidine and B(C6F5)3 is shown to mediate the catalytic hydrogenation of CO2 using H2 as the reductant and a silylhalide as an oxophile. The nature of the products can be controlled with the judicious selection of the silylhalide and the solvent. In this fashion, this metal-free catalysis affords avenues to the selective formation of the disilylacetal (R3SiOCH2OSiR3), methoxysilane (R3SiOCH3), methyliodide (CH3I) and methane (CH4) under mild conditions. DFT studies illuminate the complexities of the mechanism and account for the observed selectivity. ",

keywords = "CO hydrogenation catalysis, acetal, frustrated Lewis pair, methane, methyliodide",

author = "Tongtong Wang and Maotong Xu and Jupp, {Andrew R.} and Zheng‐Wang Qu and Stefan Grimme and Stephan, {Douglas W.}",

note = "Funding Information: D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Canada Council for the Arts and the RSC(UK) are thanked for a 2020 Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (Leibniz prize to S.G) for financial support. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. A.R.J. is grateful for the award of a Banting Fellowship for funding. Open Access funding enabled and organized by Projekt DEAL.",

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AU - Grimme, Stefan

AU - Stephan, Douglas W.

N1 - Funding Information: D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Canada Council for the Arts and the RSC(UK) are thanked for a 2020 Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (Leibniz prize to S.G) for financial support. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. A.R.J. is grateful for the award of a Banting Fellowship for funding. Open Access funding enabled and organized by Projekt DEAL.

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