The formation of iron carbonyl radical anions in the reactions of iron carbonyls with trimethylamine N-oxide

Abstract

The interaction of iron carbonyls, Fe(CO) 5, Fe 2(CO) 9 and Fe 3(CO) 12 with Me 3NO occurs according to a one-electron redox-disproportionation scheme giving rise to iron carbonyl radical anions: Fe 2(CO) 8 ·− ( 1), Fe 3(CO) 12 ·− ( 2), Fe 3(CO) 11 ·− ( 3) and Fe 4(CO) 13 ·− ( 4). The role of Me 3NO, inducing CO-substitution, consists of the generation of reactive 17-electron species with a labile coordination sphere in which the substitution for other ligands occurs, resulting from fast ligand and electron exchange in the confines of the ETC-reaction.