Pyridine- and pyrimidine-2-thiolate complexes of ruthenium

A series of mononuclear ruthenium complexes containing pyridine- and pyrimidine-2-thiolato ligands was prepared and characterized. The new compounds of general formula CpRu(PPh3)(κ2S,N-SR) (1) (SR = pyridine-2-thiolate (a), pyrimidine-2-thiolate (b)) were prepared directly by reacting the thiolato anions (RS−) with CpRu(PPh3)2Cl. Complexes 1 readily react with NOBF4 or CO in THF at room temperature to give [CpRu(PPh3)(NO)(κ1S-HSR)][BF4]2 (2) and CpRu(PPh3)(CO)(κ1S-SR) (3), respectively. The one-pot reaction of CpRu(PPh3)2Cl, thiolato anions and bis(diphenylphosphino)ethane (dppe) gave CpRu(dppe)(κ1S-SR) [dppe: Ph2PCH2CH2PPh2 (4)]. The complex salts, [CpRu(PPh3)2(κ1S-HSR)]BPh4 (5) are prepared by mixing CpRu(PPh3)2Cl, HSR and NaBPh4 at room temperature. The structures of CpRu(PPh3)(κ2S,N-Spy) (1a), [CpRu(PPh3)(NO)(κ1S-HSpy)][BF4]2 (2a) and CpRu(PPh3)(CO)(κ1S-Spy) (3a), (py = C5H4N) have been determined.