Synthesis of Heterobimetallic Fe-M (M = Ni, Pd, Pt) Complexes Containing the 1,1'-Ferrocenedithiolato Ligand and Their Conversion to Trinuclear Complexes.

The reaction of [NiCl(2)(PMe(2)Ph)(2)] with fc(SH)(2) (fcS(2) = 1,1'-ferrocenedithiolato) afforded the Ni-Fe heterobimetallic complex containing an Fe-->Ni dative bond [Ni(S(2)fc)(PMe(2)Ph)] (1) with concurrent liberation of one of the PMe(2)Ph ligands. In contrast, similar treatment of [MCl(2)(dppe)] (M = Ni, Pd, Pt; dppe = Ph(2)PCH(2)CH(2)PPh(2)) gave a series of group 10 metal-ferrocenedithiolato complexes [M(S(2)fc)(dppe)] (2) which do not contain such a dative bond. Furthermore, oxidation of complexes 2 with 1 equiv of [(eta(5)-C(5)H(5))(2)Fe][PF(6)] resulted in the formation of 1,1'-ferrocenedithiolato-bridged complexes [{M(dppe)}(2)(&mgr;-S(2)fc)]PF(6) (3) along with poly(1,1'-ferrocenylene disulfide). Complexes 2 were also converted into the Fe-Ru-M heterotrimetallic complexes [(p-cymene)RuCl(&mgr;-S(2)fc)M(dppe)][PF(6)] (4; p-cymene = 4-isopropyltoluene) by the reaction of 2 with (p-cymene)RuCl(2) and NH(4)PF(6) in acetonitrile. The detailed structures of 1, [Ni(S(2)fc)(dppe)] (2a), [Pd(S(2)fc)(dppe)] (2b), [{Ni(dppe)}(2)(&mgr;-S(2)fc)]PF(6) (3a), and [(p-cymene)RuCl(&mgr;-S(2)fc)Ni(dppe)][PF(6)] (4a) have been determined by X-ray crystallography.