Interaction of iron carbonyls with lewis bases

Abstract

The interaction of Fe n (CO) m ( n = 1, m = 5; n = 2, m 9; n = 3, m = 12) with Lewis bases taken in the anionic form (as NaL salts, where L = azolide, OR, SR, NR 2, NO 2; R 2C = NO 2, where R = H or alkyl) and in the neutral form (dimethyl sulphoxide, dimethyl formamide, pyridine, o-phenanthroline) was studied. The first stage of the reaction is the formation of an iron carbonyl-Lewis base complex. In the second stage one-electron transfer from this activated complex to the free iron carbonyl gives rise to both the Fe I complexes and the anion radicals Fe 2(CO) 8 −, Fe 3(CO) 11 −, Fe 4(CO) 13 − and Fe 3(CO) 12 −. The latter species are active particles prone to interconversions and are capable of participating in cluster-formation processes. A Water Gas Shift Reaction (WGSR) mechanism involving iron carbonyl radical anions is proposed.