Mechanism insights into the Iridium(III)- and B(C6F5)3-Catalyzed reduction of CO2 to the Formaldehyde Level with Tertiary Silanes

Guzmán, Jefferson ; Urriolabeitia, Asier (Universidad de Zaragoza) ; Padilla, Marina ; García-Orduña, Pilar ; Polo, Víctor (Universidad de Zaragoza) ; Fernández-Alvarez, Francisco J. (Universidad de Zaragoza)

Resumen: 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.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.2c03330

Año: 2022

Publicado en: Inorganic Chemistry 61, 50 (2022), 20216-20221
ISSN: 0020-1669

Factor impacto JCR: 4.6 (2022)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 5 / 42 = 0.119 (2022) - Q1 - T1

Factor impacto CITESCORE: 8.0 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.997 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MECD/FPU17-05417
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)