Synthesis and Characterization of Double- and Triple-Butterfly Fe/S Cluster Complexes Obtained from the Novel Butterfly Cluster Anions {(μ-RS)(μ-CO)[Fe₂(CO)₆]₂(μ₄-S)}^- and (μ-RS)(μ-S^-)[Fe₂(CO)₆]₃(μ₄-S)₂. Crystal Structures of (μ-MeS)(μ-PhNHCS)[Fe₂(CO)₆]₂(μ₄-S), (μ-MeS)(μ-MeSCS)[Fe₂(CO)₆]₂(μ₄-S), and (μ-PhCH₂S)₂[Fe₂(CO)₆]₃(μ₄-S)₂

Abstract

The novel reaction of (μ-RS)(μ-S-)Fe2(CO)6 (1) with Fe3(CO)12 gives a new type of anion, {(μ-RS)(μ-CO)[Fe2(CO)6]2(μ4-S)}- (4). While anions 4 (R = Me, Et) react with PhNCS/CF3CO2H to give the neutral double-cluster complexes (μ-RS)(μ-PhNHCS)[Fe2(CO)6]2(μ4-S) (6, R = Me; 7, R = Et), the reaction of 4 (R = Me, Ph, p-MeC6H4) with CS2/MeI or PhCH2Br affords the neutral double-cluster complexes (μ-RS)(μ-MeSCS)[Fe2(CO)6]2(μ4-S) (8, R = Me; 10, R = p-MeC6H4; 12, R = Ph), and (μ-RS)(μ-PhCH2SCS) [Fe2(CO)6]2(μ4-S) (9, R = Me; 11, R = p-MeC6H4), respectively. More interestingly, reaction of anions 4 with μ-S2Fe2(CO)6 produces another new type of anion, (μ-RS)(μ-S-)[Fe2(CO)6]3(μ4-S)2 (5), which reacts further with MeI, EtBr, or PhCH2Br to give the neutral triple-cluster complexes (μ-RS)(μ-MeS)[Fe2(CO)6]3(μ4-S)2 (13, R = Me; 14, R = p-MeC6H4), (μ-p-MeC6H4S)(μ-EtS)[Fe2(CO)6]3(μ4-S)2 (15), and (μ-PhCH2S)2[Fe2(CO)6]3(μ4-S)2 (16), respectively. All these new double- and triple-butterfly clusters have been characterized by combustion analyses and spectroscopy as well as by X-ray diffraction for clusters 6, 8, and 16.