SPh functionalized bridging-vinyliminium diiron and diruthenium complexes

The SPh functionalized vinyliminium complexes [Fe2{μ-η1:η3-Cγ(R′)double bond; length as m-dashCβ(SPh)Cαdouble bond; length as m-dashN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] [R = Xyl, R′ = Me, 2a; R = Me, R′ = Me, 2b; R = 4-C6H4OMe, R′ = Me, 2c; R = Xyl, R′ = CH2OH, 2d; R = Me, R′ = CH2OH, 2e; Xyl = 2,6-Me2C6H3] are generated in high yields by treatment of the corresponding vinyliminium complexes [Fe2{μ-η1:η3-Cγ(R′)double bond; length as m-dashCβ(H)Cαdouble bond; length as m-dashN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (1a–e) with NaH in the presence of PhSSPh. Likewise, the diruthenium complex [Ru2{μ-η1:η3-Cγ(Me)double bond; length as m-dashCβ(SPh)Cαdouble bond; length as m-dashN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (2f) was obtained from the corresponding vinyliminium complex [Ru2{μ-η1:η3-Cγ(Me)double bond; length as m-dashCβ(H)Cαdouble bond; length as m-dashN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (1f). The synthesis of 2c is accompanied by the formation, in comparable amounts, of the aminocarbyne complex [Fe2{μ-CN(Me)(4-C6H4OMe)}(SPh)(μ-CO)(CO)(Cp)2] (3). The molecular structures of 2d, 2e and 3 have been determined by X-ray diffraction studies.