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Frustrated Lewis Pair Catalyzed Reduction of Carbon Dioxide Using Hydroboranes: New DFT Mechanistic Insights
Author(s) -
Qu ZhengWang,
Zhu Hui,
Grimme Stefan
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202000604
Subject(s) - frustrated lewis pair , chemistry , catalysis , lewis acids and bases , borane , hydride , formate , adduct , catalytic cycle , selective reduction , acetal , combinatorial chemistry , reducing agent , medicinal chemistry , organic chemistry , metal
Catalytic CO 2 reduction is attractive for the sustainable production of value‐added fuels and chemicals. Prevented by an unclear mechanistic picture, only a few frustrated Lewis pair (FLP) catalysts are known for the efficient CO 2 reduction under mild conditions using hydroboranes as reductant. For the first time, based on extensive DFT calculations, very efficient mechanisms for all steps of the FLP‐catalyzed reduction of CO 2 to various products of boryl formate, H 2 CO, bis(boryl) acetal and methoxyl borane are revealed. Zwitterionic B/P FLP‐H 2 CO adducts are confirmed as active catalyst via the Lewis‐basic CH 2 O “oxide” center. Strong O and N Lewis‐bases are very active in promoting hydride transfer from hydroboranes to CO 2 and strongly bound to the boryl group of reduced species. This can be modulated by Lewis acids in FLP catalysts for well‐balanced catalytic activity, which is crucial for further design of novel catalytic process.