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Cobalt(I)-Catalyzed Transformation of Si–H Bonds: H/D Exchange in Hydrosilanes and Hydrosilylation of Olefins

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cris.lastimport.scopus2024-02-12T20:37:12Z
dc.abstract.enThe amino imidazolin-2-imine ligand [HAmIm, 1,2-(DippNH)–C6H4–N═C(NiPrCMe)2] is employed in the synthesis of the paramagnetic cobalt(I) arene complex Co(AmIm)(η6-C6H6). The latter was found to be a highly efficient (pre)catalyst in H/D exchange reactions with deuterium (D2) in hydrosilanes. The scope comprises primary to tertiary silanes at a low catalyst loading of 1 mol %. Additionally, the same cobalt(I) arene complex was able to catalyze hydrosilylation reactions of terminal olefins with primary to tertiary silanes at low catalyst loadings of 0.5 mol %. The scope of hydrosilylation includes intramolecular hydrosilylation to produce silacarbocycles and multiple hydrosilylation with primary silanes. The mechanistic investigation includes numerous control experiments for both H/D exchange and hydrosilylation. Isolated (trapped) cobalt(III) hydride silyl complexes (including X-ray crystallographic authentication) are presented for primary to tertiary Si–H entities, which demonstrates a wide scope of Si–H bond activation by the low-valent Co(AmIm) core. The experimental results are strongly corroborated by density functional theory calculations, which explore the possible reaction mechanisms of studied reactions.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorLopez, Juan Pablo Martinez
dc.contributor.authorTrzaskowski, Bartosz
dc.contributor.authorFrank, René
dc.contributor.authorTamm, Matthias
dc.contributor.authorŚwierczewski, Stanisław
dc.contributor.authorWullschläger, Daniela
dc.contributor.authorDenker, Lars
dc.date.accessioned2024-01-24T19:30:49Z
dc.date.available2024-01-24T19:30:49Z
dc.date.issued2023
dc.description.financePublikacja bezkosztowa
dc.description.number4
dc.description.volume13
dc.identifier.doi10.1021/ACSCATAL.2C06259
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/103184
dc.identifier.weblinkhttps://pubs.acs.org/doi/pdf/10.1021/acscatal.2c06259
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofACS Catalysis
dc.relation.pages2586-2600
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.titleCobalt(I)-Catalyzed Transformation of Si–H Bonds: H/D Exchange in Hydrosilanes and Hydrosilylation of Olefins
dc.typeJournalArticle
dspace.entity.typePublication