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 [NiCl2(PMe2Ph)2] with fc(SH)2 (fcS2 = 1,1‘-ferrocenedithiolato) afforded the Ni−Fe heterobimetallic
complex containing an Fe→Ni dative bond [Ni(S2fc)(PMe2Ph)] (1) with concurrent liberation of one of the PMe2Ph ligands. In contrast, similar treatment of [MCl2(dppe)] (M = Ni, Pd, Pt; dppe = Ph2PCH2CH2PPh2) gave a
series of group 10 metal−ferrocenedithiolato complexes [M(S2fc)(dppe)] (2) which do not contain such a dative
bond. Furthermore, oxidation of complexes 2 with 1 equiv of [(η5-C5H5)2Fe][PF6] resulted in the formation of
1,1‘-ferrocenedithiolato-bridged complexes [{M(dppe)}2(μ-S2fc)][PF6]2 (3) along with poly(1,1‘-ferrocenylene
disulfide). Complexes 2 were also converted into the Fe−Ru−M heterotrimetallic complexes [(p-cymene)RuCl(μ-S2fc)M(dppe)][PF6] (4; p-cymene = 4-isopropyltoluene) by the reaction of 2 with [(p-cymene)RuCl2]2 and
NH4PF6 in acetonitrile. The detailed structures of 1, [Ni(S2fc)(dppe)] (2a), [Pd(S2fc)(dppe)] (2b), [{Ni(dppe)}2(μ-S2fc)][PF6]2 (3a), and [(p-cymene)RuCl(μ-S2fc)Ni(dppe)][PF6] (4a) have been determined by X-ray crystallography.