Metal Derivatives of Heterocyclic-2-thiones: Crystal Structures of [Bis(diphenylphosphanyl)propane][bis(pyrimidine-2-thiolato)]ruthenium(II) and [Bis(diphenylphosphanyl)methane][bis(pyridine-2-thiolato)]ruthenium(II)

Ruthenium(II) Complexes containing pyrimidine-2-thiolate (pymS) and bis(diphenylphosphanyl)alkanes [Ph2P(CH2)mPPh2, m = 1, dppm; m = 2, dppe; m = 3, dppp; m = 4, dppb] are described. Reactions of [RuCl2L2] (L = dppm, dppp) and [Ru2Cl4L3] (L = dppb) with pyrimidine-2-thione (pymSH) in 1:2 molar ratio in dry benzene in the presence of Et3N base yielded the [Ru(pymS)2L] complexes (pymS = pyrimidine-2-thiolate; L = dppm (1); dppp (3); dppb (4)). The complex [Ru(pymS)2(dppe)] (2) was indirectly prepared by the reaction of [Ru(pymS)2(PPh3)2] with dppe. These complexes were characterized using analytical data, IR, 1H, 13C, 31P NMR spectroscopy, and X-ray crystallography (complex 3). The crystal structure of the analogous complex [Ru(pyS)2(dppm)] (5) with the ligand pyridine-2-thiolate (pyS) was also described. X-ray crystallographic investigation of complex 3 has shown two four-membered chelate rings (N, S donors) and one six-membered ring (P, P donors) around the metal atom. Compound 5 provides the first example in which RuII has three four-membered chelate rings: two made up by N, S donor ligands and one made up by P, P donor ligand. The arrangement around the metal atoms in each complex is distorted octahedral with cis:cis:trans:P, P:N, N:S, S dispositions of the donor atoms. The 31P NMR spectroscopic data revealed that the complexes are static in solution, except 2, which showed the presence of more than one species.