Reduction of nickelous acetate with sodium borohydride in ethanolic solution yields a nearly colloidal black suspension (P-2 nickel) which, used in situ, is a hydrogenation catalyst of extraordinary sensitivity to the environment of the double bond. Slight increases in hindrance are strongly reflected in the rate of hydrogenation: 1octene, 1.00; 3-methyl-1-butene, 0.23; 3,3-dimethyl-1-butene, 0.07. Substitution of the olefinic moiety more markedly affects the reduction rate: 1-octene, 1.0; 2-methyl-1-pentene, 0.004; 2-methyl-2-pentene, <<0.001; 2,3-dimethy 1-2-butene, 0. Cyclohexene is peculiarly inert among simple cyclic alkenes: cyclopentene, 1.00; cyclohexene, ~0.010; cycloheptene, 0.60; cyclooctene, 0.20. Strained double bonds are readily reduced: bicyclo[2.2.ljheptene, 1.0; cyclopentene, 0.26; cis-2-pentene, <0.01. The presence of an aryl group, even nonconjugated, markedly promotes hydrogenation: 1-octene, 1.0; 3,4-methylenedioxyallylbenzene (safrole), >3.5; allylbenzene, 3.0. Double-bond isomerization and disproportionation of cyclohexadienes are minimal. Benzylic compounds are not hydrogenolyzed significantly in 24 hr, and allylie and propargylic compounds are hydrogenated with no detectable hydrogenolysis. Dienes and acetylenes are partially reduced with high selectivity.Sodium borohydride reacts with various group VIIIB transition metals to yield finely divided black precipitates, some of which are active catalysts for hydrolysis of borohydride.3•4 567Certain of these materials have been shown to be hydrogenation catalysts