The SPh functionalized vinyliminium complexes [Fe 2 {μ-η 1 :η 3 -C γ (R′)C β (SPh)C α N(Me)(R)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ] [R=Xyl, R′=Me, 2a; R=Me, R′=Me, 2b; R=4-C 6 H 4 OMe, R′=Me, 2c; R=Xyl, R′=CH 2 OH, 2d; R=Me, R′=CH 2 OH, 2e; Xyl=2,6-Me 2 C 6 H 3 ] are generated in high yields by treatment of the corresponding vinyliminium complexes [Fe 2 {μ-η 1 :η 3 -C γ (R′)C β (H)C α N(Me)(R)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ] (1a–e) with NaH in the presence of PhSSPh. Likewise, the diruthenium complex [Ru 2 {μ-η 1 :η 3 -C γ (Me)C β (SPh)C α N(Me)(Xyl)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ] (2f) was obtained from the corresponding vinyliminium complex [Ru 2 {μ-η 1 :η 3 -C γ (Me)C β (H)C α N(Me)(Xyl)}(μ-CO)(CO)(Cp) 2 ] (1f). The synthesis of 2c is accompanied by the formation, in comparable amounts, of the aminocarbyne complex [Fe 2 {μ-CN(Me)(4-C 6 H 4 OMe)}(SPh)(μ-CO)(CO)(Cp) 2 ] (3).The molecular structures of 2d, 2e and 3 have been determined by X-ray diffraction studies.