Thiometalate Complexes Containing Arene, Thiophene, and Cyclobutadiene Coligands. Are Thiometalate Clusters Good Models for Desulfurization Catalysts?

Kevin E. Howard, John R. Lockemeyer, Mark A. Massa, Thomas B. Rauchfuss, Scott R. Wilson, Xiaoguang Yang

Research output: Contribution to journalArticlepeer-review

Abstract

Reaction of [(p-cymene)RuCl2]2 and (PPh4)2WS4 gives [(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 Ru2PtW2 compounds from ReS4- and Pt(WS4)22-, respectively. The reaction of (p-cymene)RuCl2(PPh3) and (PPh4)2WS4 gave (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)2WS4 results in the release of free tetramethylthiophene. In contrast, the p-cymene ligands were only labilized by further treatment of [(p-cymene)RuCl]2WS4 with WS42-. [(C4Me4)NiCl2]2 and WS42- give [(C4Me4)NiCl]2WS4 while (C4Me4)NiWS4(PMe2Ph) was prepared from (C4Me4)NiCl2(PMe2Ph). (C4Me4)NiWS4(PMe2Ph) crystallizes in the monoclinic space group Ia (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]2WS4 with (Me3Si)2S gives a polymeric sulfided material, which upon pyrolysis evolves tetramethylthiophene.

Original languageEnglish (US)
Pages (from-to)4385-4390
Number of pages6
JournalInorganic Chemistry
Volume29
Issue number22
DOIs
StatePublished - 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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