Hydrolysis of dinuclear ruthenium complexes [{CpRu(PPh3)2}2(m-h1:1-L)](CF3SO3)2 (L = P4, P4S3): a plane route to access unprecedented P2H4 and PH2SH metal complexes

Abstract: The reaction of [CpRu-ACHTUNGTRENUNG(PPh3)2Cl] (1) with half an equivalent of P4 or P4S3 in the presence of AgCF3SO3 as chloride scavenger affords the stable dimetal complexes [{CpRuACHTUNGTRENUNG(PPh3)2}2(m,h1:1-P4)]ACHTUNGTRENUNG[CF3SO3]2· 3CH2Cl2 (2) and [{CpRuACHTUNGTRENUNG(PPh3)2}2- ACHTUNGTRENUNG(m,h1:1-Papical-Pbasal-P4S3)]ACHTUNGTRENUNG[CF3SO3]2·0.5C7H8 (3), in which the tetrahedral P4 and mixed-cage P4S3 molecules are respectively bound to two CpRu-ACHTUNGTRENUNG(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 [{CpRuACHTUNGTRENUNG(PPh3)2}2(m,h1:1-P2H4)]ACHTUNGTRENUNG[CF3SO3]2(4) and [CpRuACHTUNGTRENUNG(PPh3)2ACHTUNGTRENUNG(h1-PH2SH)]- ACHTUNGTRENUNGCF3SO3 (8) were isolated. In the former, diphosphane, P2H4, is coordinated to two CpRuACHTUNGTRENUNG(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.