Reactions of Pt3Ru6(CO)2(μ3‐H)(μ‐H)3 with Phos[phanes — The Synthesis and Structural Characterizations of [Pt(PMe3)3H][Pt3Ru6(CO)21(μ3‐H)(μ‐H)2] and [Pt3Ru6(CO)20(PPh3)(μ‐H)3(μ3H)

Abstract

AbstractThe reactions of [Pt3Ru6(CO)21(μ‐H)3(μ3‐H)] (1) with PMe3 and PPh3 have produced the salts [Pt(PR3)3H]‐[Pt3Ru6(CO)21(μ3‐H)(μ‐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)μ‐H)3(μ3‐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(μ3‐H)(μ‐H)2]−. The anion contains a layer segregated Ru3Pt3Ru3 structure similar to that of 1 with two bridging hydride ligands on one Ru3 triangle and one semi‐triply bridging hydride ligand on the other. The cation [Pt(PR3)3H]+ 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 Ru3 and Pt3 triangles. The PPh3 ligand is coordinated to one of the ruthenium atoms in an axial position.