Synthesis of Group 10 polyfluorothiolate mono- and bi-nuclear complexes. Crystal structures of [Ni(SC 6HF 4) 2(dppe)], [(dppe)Ni(μ-SC 6HF 4) 2Pd(C 6F 5) 2] and [(dppe)Ni(μ-SC 6F 5) 2Pd(C 6F 5) 2]

• Published in: Journal of organometallic chemistry 2002-12, Vol.663 (1), p.98-107
• Main Authors: Usón, Miguel A., Llanos, Jesús M.
• Format: Article
• Language: English
• Subjects: Crystal structures; Group 10; Homo- and heterobinuclear; Organometallic compounds; Thiolates; π–π Interactions
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(02)01734-5

Complexes of the general formula cis-[M(2,3,5,6-SC 6HF 4) 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-[MCl 2(LL)] and Tl(SC 6HF 4). These compounds, when treated with cis-[M(C 6F 5) 2(THF) 2] (M=Pd, Pt; THF=OC 4H 8), 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(SC 6HF 4) 2(dppe)], [(dppe)Ni(μ-SC 6HF 4) 2Pd(C 6F 5) 2] and [(dppe)Ni(μ-SC 6F 5) 2Pd(C 6F 5) 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. Homologous complexes containing the pentafluorothiophenolate or p-tetrafluorothiophenolate ligands show very different interfacial π–π interactions between aromatic rings.