SPh functionalized bridging-vinyliminium diiron and diruthenium complexes

The SPh functionalized vinyliminium complexes [Fe(2){mu-eta(1):eta(3)-C(gamma)(R')=C(beta)(SPh)C(alpha)=N(Me)(R)}(mu-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){mu-eta(1): eta(3)-C(gamma)(R')=C(beta)(H)C(alpha)=N(Me)(R)}(mu-CO)( CO)(Cp)(2)][SO(3)CF(3)] (1a-e) with NaH in the presence of PhSSPh. Likewise, the diruthenium complex [Ru(2){mu-eta(1):eta(3)-C(gamma)(Me)=C(beta)(SPh)C(alpha)=N(Me)(Xyl)}(mu-CO)(CO)(Cp)(2)][SO(3)CF(3)] (2f) was obtained from the corresponding vinyliminium complex [Ru(2){mu-eta(1):eta(3)-C(gamma)(Me)=C(beta)(H)C(alpha)=N(Me)(Xyl)}(mu-CO)(CO)(Cp)(2)] (1f). The synthesis of 2c is accompanied by the formation, in comparable amounts, of the aminocarbyne complex [Fe(2){mu-CN(Me)(4-C(6)H(4)OMe)}(SPh)(mu-CO)(CO)(Cp)(2)] (3). The molecular structures of 2d, 2e and 3 have been determined by X-ray diffraction studies. (C) 2008 Published by Elsevier B.V.