Inorganic Chemistry, Vol.35, No.14, 4137-4147, 1996
Solvate Molecule Effects and Unusual Fe-57 Mossbauer Line Broadening in the Valence Detrapping of Mixed-Valence (Fe3O(O2Cch3)(6)(3-Et-PY)(3))Center-Dot-S
A new series of mixed-valence mu(3)-oxo-bridged Fe3O complexes with the composition [Fe3O(O2CCH3)(6)(3-Et-py)(3)]. S, where 3-Et-py is 3-ethylpyridine and the solvate molecule S is either 0.5C(6)H(5)CH(3) (1), 0.5C(6)H(6) (2), CH3CN (3), or CH3CCl3 (4), is reported. The complex [Fe3O(O2CCH3)(6)(3-Et-py)(3)]. 0.5C(6)H(5)CH(3) (1) crystallizes in the orthorhombic space group Fdd2 which at 298 K has a unit cell with a = 22.726(8) Angstrom, b = 35.643(14) Angstrom, c = 20.816(6) Angstrom, and Z = 16, Refinement with 5720 observed [F > 5 sigma(F-0)] reflections gave R = 0.0337 and R(w) = 0.0390. An analysis of the bond lengths in complex 1 shows that it is the most valence-trapped Fe3O complex reported at room temperature. The complex [Fe3O(O2CCH3)(6)(3-Et-py)(3)].
Keywords:INTRAMOLECULAR ELECTRON-TRANSFER;IRON ACETATE COMPLEXES;PHASE-TRANSITIONS;SOLID-STATE;TRANSFER RATES;HEAT-CAPACITY;VIBRATIONAL-SPECTRA;METAL-COMPLEXES;H-2 NMR;MICROMODULATION