Synthesis of cyclopentadienyl ruthenium 4-pyridine and 2-pyrimidine thiolates and their bimetallic group VI metal carbonyls

The complexes CpRu(P-P)S-4-Py (Cp = η5-C5H5; P-P = dppm (1), dppe (2); Py = pyridine) and CpRu(P-P)S-2-Pym (P-P = dppm (3), dppe (4); Pym = pyrimidine) were prepared by the one pot reaction of CpRu(PPh3)2Cl, S-het and the dppm or dppe ligand. 1 and 2 reacted with M(CO)5THF at room temperature to give CpRu(P-P)(μ-4-SPy)(M(CO)5) [P-P = dppm (5), dppe (6); M = Cr (a), Mo (b), W (c)]. The corresponding reactions of 3 and 4 with M(CO)5THF produced CpRu(P-P)(μ-2-SPym-κ2S,N)(M(CO)4) (P-P = dppm (7), dppe (8)). 1-8 have been characterized by spectroscopic methods (FT-IR, 1H and 31P NMR) and elemental analysis. The solid-state structures of 1 and 2 have been determined by X-ray crystallography.