Diferrous cyanides as models for the Fe-only hydrogenases

Christine A. Boyke, Jarl Ivar Van Der Vlugt, Thomas B. Rauchfuss, Scott R. Wilson, Giuseppe Zampella, Luca De Gioia

Research output: Contribution to journalArticlepeer-review


The first systematic study of diferrous dicyano dithiolates is described. Oxidation of [Fe2(S2C2H4)(CN) 2(CO)4]2- in the presence of cyanide and tertiary phosphines and of Fe2(S2C2H 4)-(CO)4(PMe3)2 in the presence of cyanide affords a series of diferrous cyanide derivatives that bear a stoichiometric, structural, and electronic relationship to the H oxair state of the Fe-only hydrogenases. With PPh 3 as the trapping ligand, we obtained an unsymmetrical isomer of Fe2(S2C2H4)(μ-CO)(CN) 2(PPh3)2- (CO)2, as confirmed crystallographically. This diferrous cyanide features the semibridging CO-ligand, with Fe-μC bond lengths of 2.15 and 1.85 Å. Four isomers of Fe2(S2C2H4)(μ-CO)(CN) 2(PMe3)2(CO)2 were observed, the initial product again being unsymmetrical but more stable isomers being symmetrical. DFT calculations confirm that the most stable isomers of Fe 2(S2C2H4)(μ-CO)(CN) 2(PMe3)2(CO)2 have cyanide trans to μ-CO. Oxidative decarbonylation also afforded the new tetracyanide [Fe 2(S2C2H4)(μ-CO)(CN) 4-(CO)2]2-. Insights into the oxidative decarbonylation mechanism of these syntheses come from the spectroscopic characterization of the tetracarbonyl [Fe2(S2C 2H4)(μ-CO)(CN)3(CO)3]. This species reacts with PEt3 to produce the stable adduct [Fe 2(S2C2H4)(μ-CO)(CN) 3(CO)2(PEt3)]-.

Original languageEnglish (US)
Pages (from-to)11010-11018
Number of pages9
JournalJournal of the American Chemical Society
Issue number31
StatePublished - Aug 10 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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