Redox properties of 17-electron thiolate complexes of cyclopentadienyl iron (III)

C. Díaz, E. Araya, M. A. Santa Ana

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8 Citations (Scopus)

Abstract

The redox electrochemistry of iron (III) thiolate complexes of the type [CpFe(dppe)-SR]PF6 R=CH3, C3H7, C6H5, p-C6H4Br and thiobenzothiazole has been examined by cyclic voltammetry, coulometry and spectroelectrochemistry methods. Four redox waves were observed in the range - 1.5 to + 1.5V (S.C.E) in CH2Cl2. Around 0.0 V the metal centered reduction Fe (III)→Fe (II) process was observed, while that around +0.5 V the wave observed was attributed to a ligand centered oxidation. Strongly irreversible waves of oxidation near 1.3 V were assigned to the oxidation of RSSR while a reduction wave also strongly irreversible at very high negative potential was attributed to the reduction of the RSSR free ligand, RSSR + 2e→2RS-. The redox wave observed for the disulphides compounds are discussed in terms of a reductive elimination of RSSR. Chemical and electrochemical reduction of the complexes [CpFe(dppe)-SR]PF6 was accomplished by the color changes blue → red-brown characteristic of the redox change 17e→18e.

Original languageEnglish
Pages (from-to)2225-2230
Number of pages6
JournalPolyhedron
Volume17
Issue number13-14
DOIs
Publication statusPublished - 1998

Keywords

  • Iron complexes
  • Phosphine-iron complexes
  • Redox properties
  • Thiolate

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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