A comparison of the reactions of PPh2CH2SR (R = Me, Ph) with alkyne-bridged dicobalt carbonyl complexes and with an iron dicobalt μ3-thioxo carbonyl complex

Andrew J. Edwards, Stephen R. MacK, Martin J. Mays, Chi Yu Mo, Paul R. Raithby, Moira Ann Rennie

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The reactions of Ph2PCH2SR (R = Me, Ph) in toluene with the dicobalt complexes [Co2 (μ-R1CCR2(CO)6] (R1 = R2 = CO2Me and R1 = H, R2 = CO2Me) give the monosubstituted complexes [Co2(μ-R1CCR2)(CO)5PPh 2CH2SMe] 1 and [Co2(μ- R1CCR2(CO)5PPh2CH2SPh] 2. On heating 1 and 2 in toluene solution, loss of CO leads to the bridged species [Co2(μ-R1CCR2)(μ- PPh2CH2SMe)(CO)4] 3 and [Co2 (μ -R1CCR2)(μ-PPh2CH2SPh)(CO) 4] 4. This transformation is readily reversed by treatment of 3 and 4 with CO, showing the Co-S bond in these complexes to be relatively weak. Similar reactions of Ph2PCH2SR (R = Me, Ph) with [Co2Fe(μ3-S)(CO)9], however, give only the ligand bridged species [Co2Fe(μ3-S)(μ-Ph2PCH 2SR)(CO)7] (R = Me 5 and R = Ph 6). Treatment of 5 and 6 with CO causes cleavage of the Co-S bond but, in contrast to 3 and 4, the ligand bridged species readily reform when the CO purge ceases. The structures of 3a and 6 have been confirmed by single-crystal X-ray analysis.

Original languageEnglish
Pages (from-to)243-252
Number of pages10
JournalJournal of Organometallic Chemistry
Issue number1-2
Publication statusPublished - 26 Jul 1996


  • Alkyne
  • Carbonyl
  • Cobalt
  • Iron
  • Phosphine
  • Sulfur

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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