Synthesis and Characterization of Ferrocenylchalcogenopropargyl Complexes [Fe(η⁵-C₅H₄E^ICH₂C⋮CH)₂] (E^I = Se, S) and Their Reactions To Form Unusual Ferrocenyl-Containing Metal Clusters with Eclipsed Cp Rings and New Five-Me

The new bis(chalcogenopropargyl)ferrocene complexes [Fe(η5-C5H4EICH2C⋮CH)2] (EI = Se, 1; EI = S, 2) have been prepared by treatment of the dilithiated [Fe(η5-C5H4Li)2] with Se or S powder, followed by reaction with propargyl bromide. Reaction of 1 and 2 with [Fe2M(μ3-E)2(CO)9] (E = S, Se and M = Fe, Ru) forms new clusters which feature an unusual five-membered FeEICHCCH2 ring with a π bond between the olefinic unit and the Fe atom, and the Cp rings adopt an eclipsed arrangement. The structures of 1 and [Fe(η5-C5H4EICH2C⋮CH)(η5-C5H4{Fe2M(CO)8(μ-E)(μ3-E)(EICHCCH2)})] (M = Fe, E = Se, EI = Se, 3; M = Fe, E = S, EI = Se, 4; M = Ru, E = S, EI = Se, 7) have been determined crystallographically.