SPh functionalized bridging-vinyliminium diiron and diruthenium complexes

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 ][SΟ 3 CF 3 ] [R=Xyl, R' = Me, 2a; R=Me, R' = Me, 2b; R = 4-C 6 H 4 ΟMe, 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 ] (la-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 [Ru2{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-C6H40Me))(SPh)(μ-CO )(CO)(Cp)2] (3). The molecular structures of 2d, 2e and 3 have been determined by X-ray diffraction studies.