Application of the hydro(solvo)thermal technique to the synthesis of metal carbonyl chalcogenide clusters Part 3. Synthesis, structural characterization, and spectroscopic studies of the clusters [{M(CO) 4} n(MS 4)] 2− (M  Mo, W; n=1, 2)

Abstract

The methanothermal reactions of M(CO) 6 (M  Mo, W) with Na 2S 2 gave a series of homonuclear clusters [{M(CO) 4} n (MS 4)] 2− (M=Mo, W; n=1, 2), i.e. (Ph 4P) 2[(CO) 4Mo(MoS 4)] ( I), (Ph 4P) 2[(CO) 4W(WS 4)] ( II), (Ph 4P) 2[(CO) 4Mo(MoS 4)Mo(CO) 4] ( III) and (Ph 4P) 2[(CO) 4W(WS 4)W(CO) 4] ( IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group P 1 with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, α=102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) Å 3 at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, α=102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) Å 3 at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, α=91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) Å 3 at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, α=90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) Å 3 at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO) 4 fragment while addition of another M(CO) 4 fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively.