Synthesis, Structure, and Reactivity of the Ruthenium(VI)−Nickel(II) Complex (dppe)Ni(μ3-S)2{Ru(N)Me2}2

The reaction between Ni(dppe)(SSiMe3)2 and 2 equiv of [N(n-Bu)4][Ru(N)Cl2Me2] produces ClSiMe3 and the heterometallic complex (dppe)Ni(μ3-S)2{Ru(N)Me2}2. The molecular structure of this complex shows the three metals and the two nitrido ligands in a plane with the bridging sulfur atoms above and below that plane. There is an interaction between one of the ruthenium centers and the nickel. The structure differs from that of the closely related complex (dppe)Pt(μ3-S)2{Ru(N)Me2}2, which has equivalent Pt−Ru distances and no strong metal−metal interactions. The complexes (dppe)M(μ3-S)2{Ru(N)Me2}2 (M = Pt, Pd, Ni) catalyze the oxidation of benzyl alcohol to benzaldehyde in toluene and in supercritical carbon dioxide.