The controlled pyrolysis of transition metal cluster substituted metal carboxylates, e.g., M(4)O[(CO)(9)Co3CCO2](6), where M = Co and Zn, and M'(2){(CO)(9)Co3CCOO}(4), where M' = Co, Mo, and Cu, results in the formation of high surface area, amorphous solids that are active and selective catalysts for the hydrogenation of crotonaldehyde. In contrast to conventional metal catalysts that are selective for the double bond hydrogenation, these new solids exhibit high regioselectivities for the conversion of crotonaldehyde (2-butenal) to crotyl alcohol (2-butenol). Further, the observed selectivities depend on the metal cluster carboxylate structure.