Hydrolysis of dinuclear ruthenium complexes [{CpRu(PPh3)2}2(mu,eta 1:1-L)](CF3SO3)2 (L = P4, P4S3): simple access to metal complexes of P2H4 and PH2SH

The reaction of [CpRu(PPh3)(2)Cl] (1) with half an equivalent of P-4 or P4S3 in the presence of AgCF3SO3 as chloride scavenger affords the stable dimetal complexes [{CpRu(PPh3)2}2(mu,eta(1:1)-P-4)][CF3SO3](2)center dot 3CH2Cl2 (2) and [{CpRu(PPh3)(2)}(2)- (mu,eta(1 : 1)-P-apical-P-basal-P4S3)][CF3SO3](2)center dot 0.5C(7)H(8) (3), in which the tetrahedral P-4 and mixed-cage P4S3 molecules are respectively bound to two CpRu(PPh3)(2) fragments through two phosphorus atoms. The coordinated cage molecules, at variance with the free ligands, readily react with an excess of water in THF under mild conditions. Among the hydrolysis products, the new, remarkably stable complexes [{CpRu(PPh3)(2)}(2)(mu,eta(1 : 1)-P2H4)][CF3SO3](2) (4) and [CpRu(PPh3)(2)(eta(1)-PH2SH)]- CF3SO3 (8) were isolated. In the former, diphosphane, P2H4, is coordinated to two CpRu(PPh3)2 fragments, and in the latter thiophosphinous acid, H2PSH, is coordinated to the metal centre through the phosphorus atom. All compounds were characterised by elemental analyses and IR and NMR spectroscopy. The crystal structures of 2, 3, 4 and 8 were determined by X-ray diffraction.