New class of diiron dithiolates related to the Fe-only hydrogenase active site: Synthesis and characterization of [Fe2(SR)2(CNME)7]2+

Joshua D. Lawrence, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review

Abstract

Electron-rich polyisocyano derivatives Fe2(S2CnH2n) (CO)6-χ(CNMe)χ (x ∼ 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe2(SR)2(CNMe)7] (PF6)2, a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the oxidized (H2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the μ-CX ligand, and an Fe-Fe separation of 2.61 Å. Oxidation of the phenylthiolate Fe2(SPh)2(CO)2(CNMe)4 led to mononuclear [Fe(SPh)(CNMe)5]-(PF6), which is analogous to [Fe2(SR)2(CNMe)10] (PF6)2 formed upon treatment of [Fe2(S2C3He)(CNMe)7] (PF6)2 with excess CNMe.

Original languageEnglish (US)
Pages (from-to)6193-6195
Number of pages3
JournalInorganic Chemistry
Volume41
Issue number24
DOIs
StatePublished - Dec 2 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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