Selective Catalytic Frustrated Lewis Pair Hydrogenation of CO2 in the Presence of Silylhalides

• Published in: Angewandte Chemie International Edition Vol. 60; no. 49; pp. 25771 - 25775
• Main Authors: Wang, Tongtong, Xu, Maotong, Jupp, Andrew R., Qu, Zheng‐Wang, Grimme, Stefan, Stephan, Douglas W.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.12.2021; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: acetal; Carbon dioxide; Catalysis; CO2 hydrogenation catalysis; Communication; Communications; frustrated Lewis pair; Hydrogenation; Methane; methyliodide; Reducing agents; Selectivity
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202112233

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. The frustrated Lewis pair (FLP), 2,6‐lutidine/ B(C6F5)3 mediates the catalytic reduction of CO2 using H2 and a silylhalide. Control of the silylhalide and solvent, affords selective avenues to the disilylacetal (R3SiOCH2OSiR3), methoxysilane (R3SiOCH3), methyliodide (CH3I) and methane (CH4) under mild conditions. The mechanism is studied by DFT and accounts for the observed selectivity.