Reactions of Pt3Ru6(CO)(21)(mu(3)-H)(mu-H)(3) with phosphanes - The synthesis and structural characterizations of [Pt(PMe3)(3)H][Pt3Ru6(CO)(21)(mu(3)-H)(mu-H)(2)] and [Pt3Ru6(CO)(20)(PPh3)(mu-H)(3)(mu(3)-H)]

The reactions of [Pt3Ru6(CO)(21)(mu-H)(3)(mu(3)-H)] (1) with PMe3 and PPh3 have produced the salts [Pt(PR3)(3)H][Pt3RU6(CO)(21)(mu(3)-H)(mu-H)(2)], 5a and 5d, R = Me and Ph in the yields 9% and 22%, respectively. By contrast the reaction of 1 with PPh3 in the presence of Me3NO has yielded the phosphane-substituted derivative [Pt3RU6(CO)(20)(PPh3)(mu-H)(3)(mu(3)-H)] (6) in 22% yield. Compounds 5a and 6 were characterized by single crystal X-ray diffraction analysis. Compounds 5a and 5d are salts of the anion [Pt3RU6(CO)(21)(mu 3-H)(mu-H)2](-). The anion contains a layer segregated Ru3Pt3RU3 structure similar to that of 1 with two bridging hydride ligands on one Ru-3 triangle and one semi-triply bridging hydride Ligand on the other. The cation [Pt(PR3)(3)H](+) was evidently formed by the abstraction of platinum from other molecules of 1. Compound 6 is a PPh3 derivative of the parent 1 that also contains the layer segregated stacking of Ru-3 and Pt-3 triangles. The PPh3 ligand is coordinated to one of the ruthenium atoms in an axial position.