Reactions of monoanions [(μ-RE)(μ-E)Fe_2(CO) _6]~- and dianions [(μ-E)_2Fe _2(CO)_6]~(2-) (E = Se, S) with N-substituted benzimidoyl chlorides, leading to novel butterfly Fe/E cluster complexes

摘要

We have first studied the reactions of monoanions [(μ-RE)(μ-E)Fe _2(CO)_6]~- (A, E = Se; B, E = S) with electrophile PhC(Cl)=NPh or dianions [(μ-E)_2Fe_2(CO) _6]~(2-) (C, E = Se; D, E = S) with electrophiles PhC(Cl)=NR′ (R′ = Ph, p-MeC_6H_4). While monoanion A was found to react with PhC(Cl)=NPh to give expected complexes (μ-RSe)[μ-SeC(Ph)=NPh]Fe_2(CO)_6 (1, R = Me; 2, R = Et; 3, R = m-MeC_6H_4), monoanion B was found to react with PhC(Cl)=NPh to afford unexpected complexes (μ-RS)[η~1-SC(Ph)= NPh-η~1]Fe_2(CO)_6 (4, R = Me; 5, R = Et). Furthermore, while dianion C reacted with PhC(Cl)=NR′ (R′ = Ph, p-MeC_6H_4) to give expected complexes [μ-SeC(Ph)= NR′]_2Fe_2(CO)_6 (6, R′ = Ph; 7, R′ = p-MeC_6H_4), dianion D was found to react with PhC(Cl)=NR′ (R′ = Ph, p-MeC_6H_4) to afford unexpected complexes [μ-SC(Ph)=NR′][η~1-C(Ph)=NR′- η~1]Fe_2(CO)_6 (8, R′ = Ph; 9, R′ = p-MeC_6H_4). All the new complexes 1-9 were characterized by elemental analysis and spectroscopy, and complexes 1 and 4-8 were further structurally confirmed by X-ray crystallography.