Synthesis of Group 10 polyfluorothiolate mono- and bi-nuclear complexes. Crystal structures of [Ni(SC6HF4)2(dppe)], [(dppe)Ni(μ-SC6HF4)2Pd(C6F5)2] and [(dppe)Ni(μ-SC6F5)2Pd(C6F5)2]

Complexes of the general formula cis-[M(2,3,5,6-SC6HF4)2(LL)] (M=Ni, Pd, Pt; LL=dppm [bis(diphenylphosphino)methane], dppe [1,2-bis(diphenylphosphino)ethane]) have been synthesized (yield>75%) by the reaction (1:2) between the corresponding cis-[MCl2(LL)] and Tl(SC6HF4). These compounds, when treated with cis-[M(C6F5)2(THF)2] (M=Pd, Pt; THF=OC4H8), quantitatively give rise to homo- or heterobinuclear compounds, (including two pairs of coordination position isomers). All of them have been characterized through IR, NMR and Mass spectrometries. The crystal structures of [Ni(SC6HF4)2(dppe)], [(dppe)Ni(μ-SC6HF4)2Pd(C6F5)2] and [(dppe)Ni(μ-SC6F5)2Pd(C6F5)2] have been determined, and the different interfacial π–π interactions between aromatic rings, which depend on the nature of the polyfluorothiolate ring, are analyzed.