Structure and magnetic properties of a non-heme diiron complex singly bridged by a hydroxo group

The synthesis of the first singly bridged non-heme diiron complex with a mu-hydroxo bridging ligand, [{(salten)Fe}2(OH)][B(C6H5)4].(CH3CN)x.(H2O)y (1) [H2salten = 4-azaheptane-1,7-bis(salicylideneiminate)], is reported. The complex has been characterized with X-ray crystallography, FTIR, magnetic susceptibility measurements, and M?ssbauer spectroscopy. The data have been compared with the results of DFT calculations on both 1 and a model with an unsupported mu-oxo bridge (2) to verify the formulation of the complex as a mu-hydroxo-bridged species. The X-ray structure [Fe-O(H) = 1.997(1) A and Fe-O(H)-Fe = 159 degrees ] is consistent with the DFT-optimized geometry of 1 [Fe-O(H) = 2.02 A and Fe-O(H)-Fe = 151 degrees ]; the Fe-O(H) distance in 1 is about 0.2 A longer than the Fe-O separations in the optimized geometry of 2 (1.84 A) and in the crystallographic structures of diiron(III) compounds with unsupported mu-oxo bridges (1.77-1.81 A). The formulation of 1 as a hydroxo-bridged compound is also supported by the presence of an O-H stretch band in the FTIR spectrum of the complex. The magnetic susceptibility measurements of 1 reveal antiferromagnetic exchange (J = 42 cm(-1) and H(ex) = JS(1).S(2)). Nearly the same J value is obtained by analyzing the temperature dependence of the M?ssbauer spectra (J = 43 cm(-1); other parameters: delta = 0.49 mm s(-1), DeltaE(Q) = -0.97 mm s(-1), and eta = 0.45 at 4.2 K). The experimental J values and M?ssbauer parameters agree very well with those obtained from DFT calculations for the mu-hydroxo-bridged compound (J = 46 cm(-1), delta = 0.48 mm s(-1), DeltaE(Q) = -1.09 mm s(-1), and eta = 0.35). The exchange coupling constant in 1 is distinctly different from the value J approximately 200 cm(-1) calculated for the optimized mu-oxo-bridged species, 2. The increased exchange-coupling in 2 arises primarily from a decrease in the Fe-O bond length.