Reactions of bis(hexamethylbenzene)iron(0) with carbon monoxide and with unsaturated hydrocarbons

Abstract

Thermal decomposition of bis(hexamethylbenzene)iron(0) in the presence of carbon monoxide yields a novel carbonyl iron complex, [C6(CH3)6]Fe(CO)2. The cyclohexadiene complex [C6(CH3)6]Fe(C6H8) is obtained from reaction of bis(hexamethylbenzene)iron(0) with either 1,3-cyclohexadiene or benzene, and the yield is much greater in the presence of hydrogen gas. Interaction of bis-(hexamethylbenzene)iron(0) with 2-butyne induces a catalytic cyclotrimerization to give more hexamethylbenzene. Kinetic and isotope distribution studies indicate that the primary step in these reactions is not a direct loss of one ring ligand, but rather an insertion of the iron center into one of the ligand methyl C---H bonds, leading to a benzyl hydride complex species. Mechanisms for the subsequent reactions of this iron hydride species are proposed.