Electron-rich diferrous-phosphane-thiolates relevant to Fe-only hydrogenase: Is cyanide "nature's trimethylphosphane"?

Jarl Ivar Van Der Vlugt, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review


The two-step one-pot oxidative decarhonylation of [Fe2-(S 2CH4)(CO)4(PMe3)2] (1) with [FeCp2]PF6, followed by addition of phosphane ligands, led to a series of diferrous dithiolato carbonyls 2-6. containing three or four phosphane ligands. In situ measurements indicate efficient formation of 12+ as the initial intermediate of the oxidation of 1, even when a deficiency of the oxidant was employed. Subsequent addition of PR3 gave rise to [Fe2(S2C2H4)(μ-CO) (CO)3(PMe3)3]2+ (2) and [Fe 2-(S2C2H4)(μ-CO)(CO) 2(PMe3)2(PR3)2] 2+ (R = Me 3, OMe 4) as principal products. One terminal CO ligand in these complexes was readily substituted by MeCN, and [Fe2(S 4C2H4)(μ-CO)(CO)2-(PMe 3)3(MeCN)]2+ (5) and [Fe2-(S 2C2H4)(μ-CO)(CO)(PMe3) 4(MeCN)]2+ (6) were fully characterized. Relevant to the Hrcd state of the active site of Fe-only hydrogenases, the unsymmetrical derivatives 5 and 6 feature a semibridging CO ligand trans to a labile coordination site.

Original languageEnglish (US)
Pages (from-to)90-98
Number of pages9
JournalChemistry - A European Journal
Issue number1
StatePublished - Dec 16 2005


  • Hydrogenases
  • Iron
  • Phosphanes
  • Thiolates

ASJC Scopus subject areas

  • General Chemistry


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