Add time:07/17/2019         Source:sciencedirect.com

CoX(PPh3)3 (X Cl, Br, I) exhibits a fairly high catalytic selectivity in the presence of BF3-OEt2 for the hydrogenation of conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene at ambient temperature and pressure to give 1-butene, 3-methyl-1-butene, and 1-pentene, respectively, as the main product, where the substituted double bond is preferentially hydrogenated. The rate of hydrogenation is independent of the diene concentration and proportional to the hydrogen pressure and to the catalyst concentration. Addition of AgClO4 instead of BF3-OEt2has essentially the same effect on the activity and selectivity for the hydrogenation of dienes when an analogous cobalt(I) complex, CoBr(PPh2Me)3, is used as the catalyst. It is proposed that the rate of hydrogenation is determined by a reaction of molecular hydrogen with a cationic tris(tertiary- phosphine) (diene)cobalt(I) species.

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