Mono-Substitution of iron pentacarbonyl catalyzed by polynuclear iron carbonyl anions

Abstract

The specific formation of LFe(CO) 4 (L = PPh 3, P(OPh) 3, P(OMe) 3 can be achieved by the reaction of Fe(CO) 5 with L in the presence of a catalytic amount of iron carbonyl anion. A convenient synthetic procedure was developed in which the iron carbonyl anion catalyst is generated in situ. It is shown that the mechanism does not proceed by the simple cleavage of the Fe 2(CO) 8 2− or Fe 3(CO) 11 2− anions, because triphenylphosphine reacts with these anions in the absence of Fe(CO) 5 to produce (PPh 3) 2Fe(CO) 3.