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 language | English (US) |
|---|---|
| Pages (from-to) | 3342-3347 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 92 |
| Issue number | 11 |
| State | Published - 1970 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Sulfur-bridged dimeric complexes of iron(III)
AU - Coucouvanis, D.
AU - Lippard, S. J.
AU - Zubieta, Jon A
PY - 1970
Y1 - 1970
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.
AB - 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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M3 - Article
VL - 92
SP - 3342
EP - 3347
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -