Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates†
| Autor: | Meg E. Fasulo, T. Don Tilley, Christophe Raynaud, Michael I. Lipschutz, Jian Yang, Odile Eisenstein, Eric Clot, Verònica Postils |
|---|---|
| Přispěvatelé: | Harvard Reproductive Sciences Center and Reproductive Endocrine Unit, Massachusetts General Hospital [Boston], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Univ Calif Berkeley, Dept Chem |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Silylation 010405 organic chemistry Hydride Alkene Ligand Cationic polymerization chemistry.chemical_element [CHIM.CATA]Chemical Sciences/Catalysis General Chemistry [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences 3. Good health Catalysis [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Nickel chemistry.chemical_compound Chemistry chemistry Chemical Sciences ComputingMilieux_MISCELLANEOUS Phosphine |
| Zdroj: | Chemical Science Chemical Science, The Royal Society of Chemistry, 2020, 11 (19), pp.5043-5051. ⟨10.1039/D0SC00997K⟩ Chemical science, vol 11, iss 19 |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/D0SC00997K⟩ |
| Popis: | 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)NiSiR3]+ 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. 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 hydrosilanes under mild conditions and low catalyst loadings. |
| Databáze: | OpenAIRE |
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