Ferrole-type compounds containing thiophenic or thiepinic rings in the 3,4-positions of the metallacycle

The new ferrole Fe2(CO)6[μ-η2,η4-(Fc)Cdouble bond; length as m-dashC{C(H)double bond; length as m-dashC(R)S}Cdouble bond; length as m-dashC(SiMe3)] [R = SiMe3 (1) and R = Fc (2)] and ruthenoles Ru2(CO)6[μ-η2,η4-(Me3Si)Cdouble bond; length as m-dashC{SC(Fc)double bond; length as m-dashC(H)}Cdouble bond; length as m-dashC(Fc)] 3 and Ru2(CO)6[μ-η2,η4-(Me3Si)Cdouble bond; length as m-dashC(SCtriple bond; length of mdashCFc)C(H)double bond; length as m-dashC(Fc)] 4, have been obtained from the reactions of M3(CO)12 (M = Fe, Ru) and FcCtriple bond; length of mdashCSCtriple bond; length of mdashCSiMe3 through S–C bond activations and C–C coupling reactions. Thermolysis of Ru2(CO)6[μ3-η2,η4,η3-(Me3Si)Cdouble bond; length as m-dashC{SC(Fc)double bond; length as m-dashC(SCtriple bond; length of mdashCSiMe3}Ru(CO)3}Cdouble bond; length as m-dashC(Fc)] alone and in the presence of HCtriple bond; length of mdashCFc, yielded the compounds Ru2(CO)6[μ-η2,η4-(Me3Si)Cdouble bond; length as m-dashC{SC(Fc)double bond; length as m-dashC(SCtriple bond; length of mdashCSiMe3)}Cdouble bond; length as m-dashC(Fc)] 5 and Ru2(CO)6[μ-η2,η4-(Me3Si)Cdouble bond; length as m-dashC{SC(Fc)double bond; length as m-dashC(SCtriple bond; length of mdashCSiMe3)C(H)double bond; length as m-dashC(Fc)}Cdouble bond; length as m-dashC(Fc)] 6, respectively. The crystal structures of the compounds 1, 3, 4 and 6 are reported.