PREPARATION AND REACTIONS OF SULFIDO AND PERSULFIDO COMPLEXES OF (PENTAMETHYLCYCLOPENTADIENYL)TUNGSTEN

Boron sulfide and hydrogen sulfide react with tungsten-oxo compounds to yield (?5-C5Me5)W(=S)2R (1a, R = Me; 1b, R = CH2SiMe3), (?5-C5Me5)W(=S)(?2-S2)Me (2a), and (?5-C5Me5)W(=O)(?2-S2)Me (3). Thiophiles such as PPh3and CN-readily abstract sulfur from the persulfido complexes 2a and 3; however, the sulfido ligands of 1a and 1b are inert to abstraction under similar conditions. In the presence of oxidizing agents, 1a undergoes intermolecular transfer of sulfur, giving 2a and (?5-C5Me5)W(=O)(=S)Me. Compound 1b crystallizes in the monoclinic space group P21/c with a = 10.967 (2) Å, b = 9.323 (1) Å, c = 18.092 (3) Å, V = 1843.8 Å3, and Z = 4. Anisotropic refinement of all non-hydrogen atoms and inclusion of hydrogen atoms at calculated positions converged to the residuals R1, = 0.027 and R2= 0.035. © 1990, American Chemical Society. All rights reserved.