Multitemperature Resonance-Diffraction and Structural Study of the Mixed-Valence Complex [Fe(3)O(OOCC(CH(3))(3))(6)(C(5)H(5)N)(3)

Abstract

The Fe-O and Fe-N bond lengths at two iron sites of the mixed-valence complex [Fe(3)O(OOCC(CH(3))(3))(6)(C(5)H(5)N)(3)] show a pronounced temperature dependence; the bonds from two of the Fe atoms to the central oxygen atoms vary by more than 0.10 Å on cooling to 10 K whereas the bond from the third iron atom is essentially invariant. The variation is such that the longest Fe-O bonds at ambient temperature are the shorter ones at 10 K, with the crossover occurring at about 90 K. The bonds to the axial pyridine ligand show the opposite dependence. The variation is attributed to an equilibrium between different configurations, which interconvert through vibronic coupling, a process that involves electron transfer between the metal atoms. The position of the absorption edge for each of the iron atoms has been determined by resonance-diffraction experiments at the Fe K edge, performed at four different temperatures. At each temperature, the order of the absorption edges corresponds to that of the experimentally determined bond lengths. The crossover near 90 K is confirmed by the resonance experiments. The absorption-edge positions are related to the formal oxidation state by calibration with reference complexes of known oxidation state. The experiments demonstrate the close relation between the changes in coordination geometry and the oxidation states of the iron atoms.