Isolation and Reactivity of Tetrylene‐Tetrylone‐Iron Complexes Supported by Bis(N‐Heterocyclic Imine) Ligands

The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl](2) (IPrN=bis(2,6‐diisopropylphenyl)imidazolin‐2‐iminato) with one equivalent of Collman's reagent (Na(2)Fe(CO)(4)) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl](2) with Na(2)Fe(CO)(4) (1 equiv) resulted in the Fe(CO)(4)‐bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene‐tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl](2) with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.