Thermal decomposition of (C6Me6)Ru(η4-C4Me4S) and related reactivity and structural studies

Shifang Luo, Thomas B. Rauchfuss, Arnold L. Rheingold

Research output: Contribution to journalArticlepeer-review


The paper focuses on selected aspects of the chemical behavior of (C6Me6)Ru(η4-C4Me4S) (1). Thermal decomposition of 1 in saturated hydrocarbon solutions yields the trinuclear product (C6Me6)3Ru3(C4Me4S)2 (2a) which has been further characterized by single crystal X-ray diffraction. The molecule is centrosymmetric with two (C6Me6)Ru(C4Me4S) entities coordinated through their sulfur atoms to a central (C6Me6)Ru unit. When the thermolysis is conducted in aromatic solvents, we also observed products resulting from arene exchange such as (arene)C6Me6)2Ru3(C4Me4S)2, where arene = C6 D6 (2b), toluene (2c). The (C6Me6)3 and arene-exchange products are formed competitively, not consecutively. Compound 2a is protonated by NH4PF6 to give the hydride [(C6Me6)3Ru3(C4Me4S)2H][PF6] ([2aH]PF6). Compound 2aH+ is structurally dynamic in solution resulting from restricted rotation about the RuS axis. Compound 1 decomposes in the presence of H2 to give the dinuclear dihydride (C6Me6)2Ru2(C4Me4S)H2 (3), assigned an unsymmetrical structure where one (C6Me6)Ru center is bound to two hydrides and a sulfur atom, while the second (C6Me6)Ru is coordinated in an η4-mode to the thiophene.

Original languageEnglish (US)
Pages (from-to)295-302
Number of pages8
JournalJournal of Organometallic Chemistry
Issue number1-2
StatePublished - Jun 14 1994


  • Arene
  • Desulfurization
  • Ruthenium
  • Sandwich complex
  • Sulfur
  • Thiophene

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry


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