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

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 t...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-12, Vol.60 (49), p.25771-25775
Main Authors: Wang, Tongtong, Xu, Maotong, Jupp, Andrew R., Qu, Zheng‐Wang, Grimme, Stefan, Stephan, Douglas W.
Format: Article
Language:English
Subjects:
acetal
Carbon dioxide
Catalysis
CO2 hydrogenation catalysis
Communication
Communications
frustrated Lewis pair
Hydrogenation
Methane
methyliodide
Reducing agents
Selectivity
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202112233