Sulfur-Bridged Dimeric Complexes of Iron (III)

D. Coucouvanis, S. J. Lippard, J. A. Zubieta

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45 Scopus citations

Abstract

Iron(III) dimers of general formula [Fe(S2CSR)2(SR)]2, R = C2H5, n-C3H7,n-C4H9, C6H5CH2, have been synthesized. Under identical conditions, only the known monomeric compound [Fe(S2CSR)3] has been isolated for R = t-C4H9. Molecular weight and proton nmr spectral studies of the diamagnetic dimers in solution have been carried out. The pmr spectrum of the ethyl dimer, assigned on the basis of spin-decoupling experiments, is consistent with a structure which contains bridging ethyl sulfide and both bridging and terminal ethyl thioxanthate ligands. Cyclic voltammetric and conventional polarographic studies of the metal-metal bonded dimers reveal a two-electron reduction wave and a one-electron oxidation wave, both irreversible. Tris(t-butylthioxan-thato)iron(III) is monomeric in solution and exhibits reversible one-electron oxidation and one-electron reduction waves. The complex contains low-spin iron(III) with an effective moment of 2.46 BM at room temperature in the solid and over the limited temperature range, 210° < T < 293 °K, in dichloromethane solution. The solid-state reflectance and solution electronic spectra of all the dimers are nearly identical, implying similar structures, but differ significantly from the corresponding spectra of the t-butyl monomer. Infrared spectra are reported and discussed.

Original languageEnglish (US)
Pages (from-to)3342-3347
Number of pages6
JournalJournal of the American Chemical Society
Volume92
Issue number11
DOIs
StatePublished - Jun 1 1970
Externally publishedYes

ASJC Scopus subject areas

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

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