127628 20231006143255.0 doi 10.1002/cctc.201901687 sideral 115851 ART-2019-115851 eng Ojeda-Amador, A.I. Mechanistic insights on the functionalization of CO2 with amines and hydrosilanes catalyzed by a Zwitterionic iridium carboxylate-functionalized bis-NHC catalyst 2019 Access copy available to the general public Unrestricted The zwitterionic complex [Cp*IrCl{(MeIm)2CHCOO}] (1) efficiently catalyzes the selective hydrosilylation of CO2 to afford the corresponding silylformate. The best reaction performance has been achieved in acetonitrile at 348 K using HSiMe2Ph. The 1-catalyzed reaction of pyrrolidine with CO2 and HSiMe2Ph strongly depends on the CO2 pressure. At low concentration of CO2 (1 bar) formation of the corresponding silylcarbamate, by insertion of CO2 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 CO2 with pyrrolidine and HSiMe2Ph has been observed, and its role in the formation of 1-formylpyrrolidine rationalized. Moreover, a mechanism for the reaction of CO2 with hydrosilanes, in the presence and in the absence of amines, based on theoretical calculations has been proposed. info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R info:eu-repo/grantAgreement/ES/MCIU/FPU14-06003 info:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-P info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.853 2019 CHEMISTRY, PHYSICAL 50 / 159 = 0.314 2019 Q2 T1 1.338 2019 Catalysis 2019 Q1 Physical and Theoretical Chemistry 2019 Q1 Organic Chemistry 2019 Q1 Inorganic Chemistry 2019 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Munarriz, J. Universidad de Zaragoza (orcid)0000-0001-6089-6126 Alamán-Valtierra, P. Universidad de Zaragoza Polo, V. Puerta-Oteo, R. Jiménez, M.V. Universidad de Zaragoza (orcid)0000-0002-0545-9107 Fernández-Alvarez, F.J. Universidad de Zaragoza (orcid)0000-0002-0497-1969 Pérez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 1009 617 Universidad de Zaragoza Dpto. Patología Animal Área Medicina y Cirugía Animal 11, 22 (2019), 5524-5535 ChemCatChem ChemCatChem 1867-3880 1229362 http://zaguan.unizar.es/record/127628/files/texto_completo.pdf Postprint 2803793 http://zaguan.unizar.es/record/127628/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:127628 articulos driver 2023-10-06-14:06:16 ARTICLE