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Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates

A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl](+), is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of...

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Autores principales: Yang, Jian, Postils, Verònica, Lipschutz, Michael I., Fasulo, Meg, Raynaud, Christophe, Clot, Eric, Eisenstein, Odile, Tilley, T. Don
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159242/
https://www.ncbi.nlm.nih.gov/pubmed/34122961
http://dx.doi.org/10.1039/d0sc00997k
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author Yang, Jian
Postils, Verònica
Lipschutz, Michael I.
Fasulo, Meg
Raynaud, Christophe
Clot, Eric
Eisenstein, Odile
Tilley, T. Don
author_facet Yang, Jian
Postils, Verònica
Lipschutz, Michael I.
Fasulo, Meg
Raynaud, Christophe
Clot, Eric
Eisenstein, Odile
Tilley, T. Don
author_sort Yang, Jian
collection PubMed
description A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl](+), is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of two coupled catalytic cycles based on [(NPN)NiH](+) and [(NPN)NiSiR(3)](+) active species, with the latter being more efficient for producing the product. The preferred silyl-based catalysis is not due to a more facile insertion of alkene into the Ni–Si (vs. Ni–H) bond, but by consistent and efficient conversions of the hydride to the silyl complex.
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spelling pubmed-81592422021-06-11 Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates Yang, Jian Postils, Verònica Lipschutz, Michael I. Fasulo, Meg Raynaud, Christophe Clot, Eric Eisenstein, Odile Tilley, T. Don Chem Sci Chemistry A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl](+), is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of two coupled catalytic cycles based on [(NPN)NiH](+) and [(NPN)NiSiR(3)](+) active species, with the latter being more efficient for producing the product. The preferred silyl-based catalysis is not due to a more facile insertion of alkene into the Ni–Si (vs. Ni–H) bond, but by consistent and efficient conversions of the hydride to the silyl complex. The Royal Society of Chemistry 2020-04-24 /pmc/articles/PMC8159242/ /pubmed/34122961 http://dx.doi.org/10.1039/d0sc00997k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Yang, Jian
Postils, Verònica
Lipschutz, Michael I.
Fasulo, Meg
Raynaud, Christophe
Clot, Eric
Eisenstein, Odile
Tilley, T. Don
Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title_full Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title_fullStr Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title_full_unstemmed Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title_short Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
title_sort efficient alkene hydrosilation with bis(8-quinolyl)phosphine (npn) nickel catalysts. the dominant role of silyl-over hydrido-nickel catalytic intermediates
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159242/
https://www.ncbi.nlm.nih.gov/pubmed/34122961
http://dx.doi.org/10.1039/d0sc00997k
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