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Alkene Hydrosilylation Using Tertiary Silanes with alpha-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts

Author(s): Pappas, Iraklis; Treacy, Sean; Chirik, Paul J

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dc.contributor.authorPappas, Iraklis-
dc.contributor.authorTreacy, Sean-
dc.contributor.authorChirik, Paul J-
dc.date.accessioned2025-02-13T15:44:12Z-
dc.date.available2025-02-13T15:44:12Z-
dc.date.issued2016-05-24en_US
dc.identifier.citationPappas, Iraklis, Treacy, Sean, Chirik, Paul J. (2016). Alkene Hydrosilylation Using Tertiary Silanes with alpha-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts. ACS CATALYSIS, 6 (4105 - 4109. doi:10.1021/acscatal.6b01134en_US
dc.identifier.issn2155-5435-
dc.identifier.urihttp://arks.princeton.edu/ark:/88435/pr13b5w825-
dc.description.abstractCombination of the readily available α-diimine ligand, ((ArN═C(Me))2 Ar = 2,6-iPr2–C6H3), (iPrDI) with air-stable nickel(II) bis(carboxylates) generated a highly active catalyst exhibiting anti-Markovnikov selectivity for the hydrosilylation of alkenes with a variety of industrially relevant tertiary alkoxy- and siloxy-substituted silanes. A combination of the method of continuous variations with stoichiometric studies identified the formally Ni(I) hydride dimer, [(iPrDI)NiH]2 as the nickel compound formed following reduction of the carboxylate ligands. For the hydrosilylation of 1-octene with (EtO)3SiH, a rate law of [Ni]1/2[1-octene][(EtO)3SiH] in combination with deuterium-labeling studies establish dissociation of the nickel hydride dimer followed by fast and reversible alkene insertion into (iPrDI)NiH, consistent with turnover-limiting C–Si bond formation. The hydrosilylation of 1-octene with triethoxysilane, a reaction performed commercially in the silicones industry on a scale of >5 000 000 kg/year, was conducted on a 10 g scale with 96% yield and >98% selectivity for the desired product. Silicone cross-linking, another major industrial application of homogeneous hydrosilylation, was also demonstrated using the air-stable nickel and ligand precursors.en_US
dc.format.extent4105 - 4109en_US
dc.language.isoen_USen_US
dc.relation.ispartofACS CATALYSISen_US
dc.rightsFinal published version. This is an open access article.en_US
dc.titleAlkene Hydrosilylation Using Tertiary Silanes with alpha-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalystsen_US
dc.typeJournal Articleen_US
dc.identifier.doidoi:10.1021/acscatal.6b01134-
pu.type.symplectichttp://www.symplectic.co.uk/publications/atom-terms/1.0/journal-articleen_US

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