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 Field | Value | Language |
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dc.contributor.author | Pappas, Iraklis | - |
dc.contributor.author | Treacy, Sean | - |
dc.contributor.author | Chirik, Paul J | - |
dc.date.accessioned | 2025-02-13T15:44:12Z | - |
dc.date.available | 2025-02-13T15:44:12Z | - |
dc.date.issued | 2016-05-24 | en_US |
dc.identifier.citation | Pappas, 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.6b01134 | en_US |
dc.identifier.issn | 2155-5435 | - |
dc.identifier.uri | http://arks.princeton.edu/ark:/88435/pr13b5w825 | - |
dc.description.abstract | Combination 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.extent | 4105 - 4109 | en_US |
dc.language.iso | en_US | en_US |
dc.relation.ispartof | ACS CATALYSIS | en_US |
dc.rights | Final published version. This is an open access article. | en_US |
dc.title | Alkene Hydrosilylation Using Tertiary Silanes with alpha-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts | en_US |
dc.type | Journal Article | en_US |
dc.identifier.doi | doi:10.1021/acscatal.6b01134 | - |
pu.type.symplectic | http://www.symplectic.co.uk/publications/atom-terms/1.0/journal-article | en_US |
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