Selective Catalytic Frustrated Lewis Pair Hydrogenation of CO 2 in the Presence of Silylhalides.

Autor: Wang T; Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.; School of Chemistry, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, China., Xu M; Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada., Jupp AR; Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada., Qu ZW; Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115, Bonn, Germany., Grimme S; Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115, Bonn, Germany., Stephan DW; Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Dec 01; Vol. 60 (49), pp. 25771-25775. Date of Electronic Publication: 2021 Nov 03.
DOI: 10.1002/anie.202112233
Abstrakt: The frustrated Lewis pair (FLP) derived from 2,6-lutidine and B(C 6 F 5 ) 3 is shown to mediate the catalytic hydrogenation of CO 2 using H 2 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 (R 3 SiOCH 2 OSiR 3 ), methoxysilane (R 3 SiOCH 3 ), methyliodide (CH 3 I) and methane (CH 4 ) under mild conditions. DFT studies illuminate the complexities of the mechanism and account for the observed selectivity.
(© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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