Reactions of unsaturated nickel-tungsten and nickel-molybdenum complexes with organic disulfides. Synthetic and structural studies

Abstract

The behavior of the unsaturated complex ([eta]-C[sub 5]Me[sub 5])Ni-W(CO)[sub 3]([eta]-C[sub 5]H[sub 4]Me) (Ni-W, 1) toward selected chalcogenide-containing ligands is described. The Ni-W species is inert to Me[sub 2]S under ambient reaction conditions, but disulfides and diselenides react with 1. Diphenyl disulfide, dimethyl disulfide, and diphenyl diselenide oxidatively add across the mixed-metal bond to afford ([eta]-C[sub 5]Me[sub 5])Ni([mu]-CO)([mu]-ER)W(CO)(ER)([eta]-C[sub 5]H[sub 4]Me) (Ni-W; Er = SPh, SMe, SePh), which contain bridging and terminal thiolate or selenate ligands. A similar Ni-Mo product was formed when ([eta]-C[sub 5]Me[sub 5])Ni-Mo(CO)[sub 3]([eta]-C[sub 5]H[sub 4]Me) was treated with PhS[sub 2]Ph. In most cases the reactions are clean, but [([eta]-C[sub 5]Me[sub 5])Ni([mu]-SePh)][sub 2] was also isolated in the diphenyl diselenide reaction. All the complexes are fluxional on the NMR time scale. The bis(benzenethiolate) nickel-tungsten species was studied by VT [sup 1]H NMR: some dynamic behavior was arrested at [minus]80[degrees]C. Structures of ([eta]-C[sub 5]Me[sub 5])Ni([mu]-CO)([mu]-CO)([mu]-SPh)W(CO)(SPh)([eta]-C[sub 5]H[sub 4]Me) (Ni-W, 2a) and [([eta]-C[sub 5]Me[sub 5])Ni([mu]-SePh)][sub 2] (3) were ascertained by single-crystal X-ray diffraction studies. 26 refs., 4 figs., 6 tabs.