THIOMETALATE COMPLEXES CONTAINING ARENE, THIOPHENE, AND CYCLOBUTADIENE COLIGANDS - ARE THIOMETALATE CLUSTERS GOOD MODELS FOR DESULFURIZATION CATALYSTS

Reaction of [(p-cymene)RuCl2]2 and (PPh4)2WS4gives [(p-cymene)RuCl]2WS4; the corresponding (C6Me6)Ru and (p-cymene)Os derivatives were also prepared. 1H NMR and IR data suggest that these compounds comprise pairs of pseudooctahedral metal centers bridged by the tetrahedral WS4. Related syntheses gave RuRe and Ru2PtW2compounds from ReS4− and Pt(WS4)22−, respectively. The reaction of (p-cymene)RuCI2(PPh3) and (PPh4)2WS4gave (p-cymene)RuWS4(PPh3), whose structure was verified by X-ray crystallography. (p-cymene)RuWS4(PPh3) crystallizes in the monoclinic space group P21/c (No. 14) with a = 9.254 (3) Å, b = 15.690 (8) Å, c = 20.102 (9) Å, β = 98.77 (3)°, and Z = 4. The analogous reaction of (tetramethylthiophene)-RuCl2(PPh3) and (PPh4)2WS4results in the release of free tetramethylthiophene. In contrast, the p-cymene ligands were only labilized by further treatment of [(p-cymene)RuCl]2WS4with WS42−. [(C4Me4)NiCl2]2 and WS42−give [(C4Me4)NiCl]2WS4while (C4Me4)NiWS4(PMe2Ph) was prepared from (C4Me4)NiCl2(PMe2Ph). (C4Me4)NiWS4(PMe2Ph) crystallizes in the monoclinic space group 1a (No. 9) with a = 13.294 (6) Å, b = 25.519 (11) Å, c = 13.186 (6) Å, β = 97.44°, and Z = 8. Treatment of [(C4Me4)NiCl]2WS4with (Me3Si)2S gives a polymeric sulfided material, which upon pyrolysis evolves tetramethylthiophene. © 1990, American Chemical Society. All rights reserved.