Syntheses, Crystal Structures, Spectroscopic Characterization, and Electrochemical Studies of the Ditungsten(III) Complexes Cl(3)W(&mgr;-L)(3)WCl(3) and [Cl(3)W(&mgr;-L)(2)(&mgr;-Cl)WCl(3)](-) (L = 1,4-Dithiane, 1,4-Thioxane, pms = Pentamethylene Sulfide). C-S Bond Cleavage of the Bridging Thioether(s) in Cl(3)W(&mgr;-L)(3)WCl(3).

Reduction of WCl(4) with 1 equiv of sodium amalgam, in the presence of either a refluxing toluene or neat solution of the desired thioether, produces a mixture of Cl(3)W(&mgr;-L)(3)WCl(3) (L = 1,4-dithiane (1), 1,4-thioxane (2), pms = pentamethylene sulfide (3)) and [Na][Cl(3)W(&mgr;-L)(2)(&mgr;-Cl)WCl(3)] (L = 1,4-dithiane (4), 1,4-thioxane (5), pms (6)). 4 and 5 could be converted to 1 and 2, respectively, in the presence of excess L in refluxing toluene. The structures of 1, 2, 3, 7, and 8 have been solved.