doi:10.1021/acs.inorgchem.2c03330engGuzmán, JeffersonUrriolabeitia, AsierPadilla, MarinaGarcía-Orduña, PilarPolo, VíctorFernández-Alvarez, Francisco J.Mechanism insights into the Iridium(III)- and B(C6F5)3-Catalyzed reduction of CO2 to the Formaldehyde Level with Tertiary SilanesART-2022-132648The 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.2022http://zaguan.unizar.es/record/13033710.1021/acs.inorgchem.2c03330http://zaguan.unizar.es/record/130337oai:zaguan.unizar.es:130337info:eu-repo/grantAgreement/ES/MECD/FPU17-05417info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00Inorganic Chemistry 61, 50 (2022), 20216-20221byhttp://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccess