Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ 4 -diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C-O bond cleavage

Christopher L. Rock, Ryan Trovitch

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2 Scopus citations


The phosphine-substituted α-diimine Ni precursor, ( Ph 2 PPr DI)Ni, has been found to catalyze alkene hydrosilylation in the presence of Ph 2 SiH 2 with turnover frequencies of up to 124 h −1 at 25 °C (990 h −1 at 60 °C). Moreover, the selective hydrosilylation of allylic and vinylic ethers has been demonstrated, even though ( Ph 2 PPr DI)Ni is known to catalyze allyl ester C-O bond hydrosilylation. At 70 °C, this catalyst has been found to mediate the hydrosilylation of ten different gem-olefins, with turnover numbers of up to 740 under neat conditions. Prior and current mechanistic observations suggest that alkene hydrosilylation takes place though a Chalk-Harrod mechanism following phosphine donor dissociation.

Original languageEnglish (US)
Pages (from-to)461-467
Number of pages7
JournalDalton Transactions
Issue number2
StatePublished - Jan 1 2019


ASJC Scopus subject areas

  • Inorganic Chemistry

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