Sulfur-bridged dimeric complexes of iron(III)

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

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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-butylthioxanthato)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
StatePublished - 1970
Externally publishedYes

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Sulfur
Dimers
Iron
Electrons
Metals
Temperature
Methylene Chloride
Sulfides
Oxidation
Dichloromethane
Protons
Molecular Weight
Ligands
Monomers
Molecular weight
Infrared radiation
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Sulfur-bridged dimeric complexes of iron(III). / Coucouvanis, D.; Lippard, S. J.; Zubieta, Jon A.

In: Journal of the American Chemical Society, Vol. 92, No. 11, 1970, p. 3342-3347.

Research output: Contribution to journalArticle

Coucouvanis, D, Lippard, SJ & Zubieta, JA 1970, 'Sulfur-bridged dimeric complexes of iron(III)', Journal of the American Chemical Society, vol. 92, no. 11, pp. 3342-3347.
Coucouvanis, D. ; Lippard, S. J. ; Zubieta, Jon A. / Sulfur-bridged dimeric complexes of iron(III). In: Journal of the American Chemical Society. 1970 ; Vol. 92, No. 11. pp. 3342-3347.
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N2 - 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-butylthioxanthato)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.

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