Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes

[Image: see text] The catalytic system [Ir(CF(3)CO(2))(κ(2)-NSi(Me))(2)] [1; NSi(Me) = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C(6)F(5))(3) promotes the selective reduction of CO(2) with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that spe...

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Autores principales: Guzmán, Jefferson, Urriolabeitia, Asier, Padilla, Marina, García-Orduña, Pilar, Polo, Víctor, Fernández-Alvarez, Francisco J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10468102/
https://www.ncbi.nlm.nih.gov/pubmed/36472385
http://dx.doi.org/10.1021/acs.inorgchem.2c03330
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author Guzmán, Jefferson
Urriolabeitia, Asier
Padilla, Marina
García-Orduña, Pilar
Polo, Víctor
Fernández-Alvarez, Francisco J.
author_facet Guzmán, Jefferson
Urriolabeitia, Asier
Padilla, Marina
García-Orduña, Pilar
Polo, Víctor
Fernández-Alvarez, Francisco J.
author_sort Guzmán, Jefferson
collection PubMed
description [Image: see text] The catalytic system [Ir(CF(3)CO(2))(κ(2)-NSi(Me))(2)] [1; NSi(Me) = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C(6)F(5))(3) promotes the selective reduction of CO(2) with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that species [Ir(CF(3)COO-B(C(6)F(5))(3))(κ(2)-NSi(Me))(2)] (3), [Ir(κ(2)-NSi(Me))(2)][HB(C(6)F(5))(3)] (4), and [Ir(HCOO-B(C(6)F(5))(3))(κ(2)-NSi(Me))(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(C(6)F(5))(3)-catalyzed hydrosilylation of CO(2) to bis(silyl)acetal is a boron-promoted Si–H bond cleavage via an iridium silylacetal borane adduct.
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spelling pubmed-104681022023-08-31 Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes Guzmán, Jefferson Urriolabeitia, Asier Padilla, Marina García-Orduña, Pilar Polo, Víctor Fernández-Alvarez, Francisco J. Inorg Chem [Image: see text] The catalytic system [Ir(CF(3)CO(2))(κ(2)-NSi(Me))(2)] [1; NSi(Me) = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C(6)F(5))(3) promotes the selective reduction of CO(2) with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that species [Ir(CF(3)COO-B(C(6)F(5))(3))(κ(2)-NSi(Me))(2)] (3), [Ir(κ(2)-NSi(Me))(2)][HB(C(6)F(5))(3)] (4), and [Ir(HCOO-B(C(6)F(5))(3))(κ(2)-NSi(Me))(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(C(6)F(5))(3)-catalyzed hydrosilylation of CO(2) to bis(silyl)acetal is a boron-promoted Si–H bond cleavage via an iridium silylacetal borane adduct. American Chemical Society 2022-12-06 /pmc/articles/PMC10468102/ /pubmed/36472385 http://dx.doi.org/10.1021/acs.inorgchem.2c03330 Text en © 2022 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Guzmán, Jefferson
Urriolabeitia, Asier
Padilla, Marina
García-Orduña, Pilar
Polo, Víctor
Fernández-Alvarez, Francisco J.
Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title_full Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title_fullStr Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title_full_unstemmed Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title_short Mechanism Insights into the Iridium(III)- and B(C(6)F(5))(3)-Catalyzed Reduction of CO(2) to the Formaldehyde Level with Tertiary Silanes
title_sort mechanism insights into the iridium(iii)- and b(c(6)f(5))(3)-catalyzed reduction of co(2) to the formaldehyde level with tertiary silanes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10468102/
https://www.ncbi.nlm.nih.gov/pubmed/36472385
http://dx.doi.org/10.1021/acs.inorgchem.2c03330
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