Formation and Reactions of Novel Types of Bridging Sulfido Anions, (μ-RE)(μ-S-)[Fe2(CO)6]2(μ4-S) (E = S, Se): Synthesis and Structures of Double- and Triple-Butterfly Fe/E Cluster Complexes

The [Et 3 NH] + salts of novel anions (μ-RE)(μ-S - )[Fe 2 (CO) 6 ] 2 (μ 4 -S) (RE = t -BuS, p -MeC 6 H 4 Se) have been prepared by reaction of [(μ-RE)(μ-CO)Fe 2 (CO) 6 ][Et 3 NH] with (μ-S 2 )Fe 2 (CO) 6 . While these salts react in situ with MeI to yield the double clusters [(μ-RE)Fe 2 (CO) 6 ](μ 4 -S)[(μ-MeS)Fe 2 (CO) 6 ], their reactions with SO 2 Cl 2 in the presence of excess [(μ-RE)(μ-CO)Fe 2 (CO) 6 ][Et 3 NH] afford the triple clusters [(μ-RE)Fe 2 (CO) 6 ] 2 [(μ 4 -S)(Fe 2 (CO) 6 ) 2 (μ 4 -S)].