Chloride substitution of [CpRu(dppf)Cl] with sulfur-containing ligands

The reactions of CpRu(dppf)Cl (1) with the sulfur-containing ligands, thiophenol HSPh, 2-mercaptopyridine C5H4N(SH), thiourea SC(NH2)2, vinylene trithiocarbonate SCS(CH)2S and ethylene trithiocarbonate SCS(CH2)2S, yielded chloro-substituted derivatives, viz. the mono-ruthenium(II) complexes CpRu(dppf)(SPh) (2), [CpRu(dppf)(SC5H4NH)]BPh4 (3)BPh4, [CpRu(dppf)(SC(NH2)2]PF6 (4)PF6, [CpRu(dppf)(SCS(CH)2S)]Cl (5)Cl and [CpRu(dppf)(SCS(CH2)2S)]Cl (6)Cl, respectively. Treatment of 1 with AuCl(SMe2) in the presence of NH4PF6 gave [(CpRu(dppf)(SMe2)]PF6 (7)PF6. The reaction of 1 or 6 with SnCl2 resulted in cleavage of chloro and dithiocarbonate ligands, respectively, to give CpRu(dppf)SnCl3 (8). All complexes were spectroscopically characterized and the structures of 2 and cationic complexes 4–7 were determined by single-crystal diffraction analyses.