Oxidative Addition of a Dinuclear and Divalent Vanadium Hydride to an Olefin C−H Bond, Leading to Catalytic Hydrogenation

The dinuclear and divalent hydride complex {[(Me3Si)NP(Ph)2C(H)P(Ph)2N(SiMe3)]V}2(μ-H)2 (1) performs oxidative addition to the styrene β-C−H bond, affording the novel dinuclear trivalent vanadium complex {[(Me3Si)NP(Ph)2C(H)P(Ph)2N(SiMe3)]V}2(H)(μ-H)2(μ,η1:η2-CHCHPh) (2). Room-temperature hydrogenolysis re-formed 1 and ethylbenzene in catalytic fashion. Reaction of 1 with ethylene afforded instead the mixed-valence {[(Me3Si)NP(Ph)2C(H)P(Ph)2 N(SiMe3)]V}2(μ-H)3 (3) and a mixture of 2-butene and 3-methyl-1,4-pentadiene.