Solvate Molecule Effects and Unusual (57)Fe Mössbauer Line Broadening in the Valence Detrapping of Mixed-Valence [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].S.
A new series of mixed-valence &mgr;(3)-oxo-bridged Fe(3)O complexes with the composition [Fe(3)O(O(2)CCH(3))(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), CH(3)CN (3), or CH(3)CCl(3) (4), is reported. The complex [Fe(3)O(O(2)CCH(3))(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) Å, b = 35.643(14) Å, c = 20.816(6) Å, and Z = 16. Refinement with 5720 observed [F > 5sigma(F(o))] 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 Fe(3)O complex reported at room temperature. The complex [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].CH(3)CCl(3) (4) crystallizes in the triclinic space group P&onemacr; which at 238 K has a unit cell with a = 12.764(2) Å, b = 13.1472(2) Å, c = 15.896(3) Å, alpha = 78.01(2) degrees, beta = 89.38(2) degrees, gamma = 61.38(1) degrees, and Z = 2. Refinement with 6264 observed [F > 5sigma(F(o))] reflections gave R = 0.0435 and R(w) = 0.0583. In this &mgr;(3)-oxo-bridged complex all three iron ions are inequivalent. Powder X-ray diffraction patterns taken at room temperature show that complexes 1 and 2 are isostructural and that complexes 3 and 4 are isostructural. Variable-temperature (57)Fe Mössbauer spectra were collected for all four complexes. The data for complexes 1 and 2 clearly indicate that these two complexes are totally valence trapped. On the other hand, Mössbauer spectra (43-293 K) for complexes 3 and 4 show that these two complexes become valence detrapped at temperatures near room temperature. Two doublets are seen at low temperature and they move together to become a single doublet at approximately 293 K. Examination of the line width versus temperature for each of the two components of the two doublets points to a curiosity. The two components of the "Fe(III)" doublet and the lower-velocity component of the "Fe(II)" doublet do not exhibit any line broadening, whereas the higher velocity "Fe(II)" component shows a surge in line width in the approximately 70-150 K range. Possible explanations for these unusual line width responses are discussed.
Wu
Chi-Cheng
CC
Department of Chemistry-0358, University of California at San Diego, La Jolla, California 92093-0358, Department of Chemistry, University of Delaware, Newark, Delaware 19716, and Institut für Anorganische und Analytische Chemie, Johannes Gutenberg-Universität, D-55099 Mainz, Germany.
Jang
Ho Gyeom
HG
Rheingold
Arnold L.
AL
Gütlich
Philipp
P
Hendrickson
David N.
DN