130337 20240319081029.0 doi 10.1021/acs.inorgchem.2c03330 sideral 132648 ART-2022-132648 eng Guzmán, Jefferson (orcid)0000-0001-9340-5952 Mechanism insights into the Iridium(III)- and B(C6F5)3-Catalyzed reduction of CO2 to the Formaldehyde Level with Tertiary Silanes 2022 Access copy available to the general public Unrestricted The catalytic system [Ir(CF3CO2)(κ2-NSiMe)2] [1; NSiMe = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C6F5)3 promotes the selective reduction of CO2 with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that species [Ir(CF3COO-B(C6F5)3)(κ2-NSiMe)2] (3), [Ir(κ2-NSiMe)2][HB(C6F5)3] (4), and [Ir(HCOO-B(C6F5)3)(κ2-NSiMe)2] (5) are intermediates of the catalytic process. The structure of 3 has been determined by X-ray diffraction methods. Theoretical calculations show that the rate-limiting step for the 1/B(C6F5)3-catalyzed hydrosilylation of CO2 to bis(silyl)acetal is a boron-promoted Si–H bond cleavage via an iridium silylacetal borane adduct. info:eu-repo/grantAgreement/ES/MECD/FPU17-05417 info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 4.6 2022 CHEMISTRY, INORGANIC & NUCLEAR 5 / 42 = 0.119 2022 Q1 T1 0.997 2022 Chemistry (miscellaneous) 2022 Q1 Physical and Theoretical Chemistry 2022 Q1 Inorganic Chemistry 2022 Q1 8.0 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Urriolabeitia, Asier Universidad de Zaragoza (orcid)0000-0001-9352-6922 Padilla, Marina García-Orduña, Pilar (orcid)0000-0002-7063-1292 Polo, Víctor Universidad de Zaragoza (orcid)0000-0001-5823-7965 Fernández-Alvarez, Francisco J. Universidad de Zaragoza (orcid)0000-0002-0497-1969 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 61, 50 (2022), 20216-20221 Inorg. chem. Inorganic Chemistry 0020-1669 1874121 http://zaguan.unizar.es/record/130337/files/texto_completo.pdf Versión publicada 3257247 http://zaguan.unizar.es/record/130337/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:130337 articulos driver 2024-03-18-17:01:42 ARTICLE