Article
Hydrovinylation of olefins catalyzed by cationic nickel complexes [Ni(2,4,6-Me3C6H2) (CH3CN) P2]BF4

https://doi.org/10.1016/S1381-1169(97)00082-4Get rights and content

Abstract

The hydrovinylation of several olefins and alkynes by the ionic nickel precursor trans-[Ni(2,4,6-Me3C6H2)(CH3CN)(P(CH2Ph)3)2]BF4 in THF solution was studied. The activity of the catalytic system showed strong dependence on the nature of the substrate. Only conjugated diolefins and some strained mono-olefins led to hydrovinylation products with nearly complete conversion, Selectivity was also variable: for norbornene, exo-2-vinylnorbornane (94%) was obtained selectively, whereas isoprene gay e a mixture of 9 hydrovinylation compounds. The turnover rate of the reaction at 25°C and 15 bar of initial pressure of ethylene with an olefin/[Ni] ratio of 1000/1 was 4300 h−1 for norbornene and 30 h−1 for isoprene. The chiral monodentate phc sphines, (cis-myrtanyl)diphenylphosphine and myrtenyldiphenylphosphine, were obtained. The catalytic precursors containing these phosphines were being tested in the hydrovinylation of styrene and norbornene, and the enantiomeric excess obtained was between 3–7%. Diphenylacetylene was also found to be active in the hydrovinylation reaction; cis- and trans-3,4-diphenyl-1,3-hexadiene, products of a double vinylation of the triple bond were obtained.

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