Synthesis and crystal structures of (fulvalene)W2(SH)2(CO)6, (fulvalene)W2(μ-S2)(CO)6, and (fulvalene)W2(μ-S)(CO)6: Low valent tungsten carbonyl sulfide and disulfide complexes stabilized by the briging fulvalene ligand

Kenneth B. Capps, Glenn D. Whitener, Andreas Bauer, Khalil A. Abboud, Ian M. Wasser, K. Peter C. Vollhardt, Carl D. Hoff

Research output: Contribution to journalArticle

7 Scopus citations

Abstract

Reaction of FvW2(H)2(CO)6 with 2/8S8 in THF results in rapid and quantitative formation of FvW2(SH)2(CO)6. The crystal structure of this complex is reported and shows that the two tungsten-hydrosulfide groups are on opposite faces of the fulvalene ligand in an anti configuration. Nevertheless, treatment of FvW2(SH)2(CO)6 (1) with PhN= NPh produces FvW2(μ-S2)(CO)6 (2) and Ph(H)NN(H)Ph. The crystal structure of the bridging disulfide, which cocrystallizes with 1 in a 2:1 ratio, is also described. Exposure of 2 equiv of ·CrCp*(CO)3 to 1 effects similar H atom transfers yielding 2 HCrCp*(CO)3 and 2. Attempts to obtain crystals of the latter from solutions derived from this reaction mixture furnished a third product, FvW2(μ-S)(CO)6 (3), which was analyzed crystallographically. The enthalpy of sulfur atom insertion into FvW2(H)2(CO)6, yielding 1, has been measured by solution calorimetry.

Original languageEnglish (US)
Pages (from-to)3212-3217
Number of pages6
JournalInorganic Chemistry
Volume41
Issue number12
DOIs
StatePublished - Jun 17 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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