Premium
Mechanistic Insights on the Functionalization of CO 2 with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst
Author(s) -
OjedaAmador Ana I.,
Munarriz Julen,
AlamánValtierra Pablo,
Polo Víctor,
PuertaOteo Raquel,
Jiménez M. Victoria,
FernándezAlvarez Francisco J.,
PérezTorrente Jesús J.
Publication year - 2019
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.201901687
Subject(s) - chemistry , catalysis , formamide , pyrrolidine , iridium , hydrosilylation , formate , carboxylate , acetonitrile , medicinal chemistry , reaction mechanism , surface modification , phenylsilane , polymer chemistry , photochemistry , organic chemistry
The zwitterionic complex [Cp*IrCl{(MeIm) 2 CHCOO}] ( 1 ) efficiently catalyzes the selective hydrosilylation of CO 2 to afford the corresponding silylformate. The best reaction performance has been achieved in acetonitrile at 348 K using HSiMe 2 Ph. The 1 ‐catalyzed reaction of pyrrolidine with CO 2 and HSiMe 2 Ph strongly depends on the CO 2 pressure. At low concentration of CO 2 (1 bar) formation of the corresponding silylcarbamate, by insertion of CO 2 into the Si−N bond of the in situ generated silylamine was observed, while at higher pressure (3 bar) the formamide derivative was obtained as major reaction product. The unexpected formation of pyrrolidin‐1‐ium formate as intermediate of the reaction the 1 ‐catalyzed of CO 2 with pyrrolidine and HSiMe 2 Ph has been observed, and its role in the formation of 1‐formylpyrrolidine rationalized. Moreover, a mechanism for the reaction of CO 2 with hydrosilanes, in the presence and in the absence of amines, based on theoretical calculations has been proposed.