Regiodivergent Hydrosilylation of Alkenes at Nickel: Tuning the Selectivity by Complex Stoichiometry and Silane Identity
Year: 2026
Type: article
Abstract: Herein, we show that nickel silylphosphine complexes are efficient regioselective catalysts for the hydrosilylation of alkenes. Regiospecific or regioselective diphenylsilane hydrosilylation of aromatic and aliphatic alkenes to the linear isomer is catalyzed by complexes [HNi(κ2(P,Si)-Ph2PC6H4-2-CH2SiMe2)(PPh3)2] (1), and [HNi(κ2(P,Si)-Ph2P-2-C6H4CH2SiiPr2)(PPh3)] (2), while regiospecific formation of the branched hydrosilylation product is obtained upon employment of the bisligated complex [Ni{κ2-(P,Si)-Ph2P–C6H4-2-CH2SiMe2}2] (3) with phenylsilane. Turnover numbers of up to 10,000 for the linear and 400 for the branched isomers in this study, situate these base-metal catalysts among the best catalysts reported. Mechanistic insights are consistent with nonradical pathways involving nickel hydride intermediates.
Source: Inorganic Chemistry
Institution: Mississippi State University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: Equipment: Helium Recovery Equipment: Efficient Recycling and Reuse of Liquid Helium in the Mississippi State University NMR Facility, G2350382153, Particle Physics Research with the CMS Experiment, MRI: Acquisition of the First 800 MHz NMR with Cryoprobe in the State of Mississippi for Biological and Chemical Research and Teaching, Research Experience for Undergraduates: Innovations at the Nexus of Food, Energy and Water Security, Highly Robust Transition Metal Complexes with E-Substituted Phosphines (E = Si, Ge, Sn) Grafted onto Metal-Organic Frameworks for Dehydrogenative Functionalization, G8530817836, G996945260
OpenAlex ID: W7164585169