Three-Coordinate Terminal Imidoiron(III) Complexes: Structure, Spectroscopy, and Mechanism of Formation
2010-07-05T00:00:00Z (GMT) by
Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFeNAd (L = bulky β-diketiminate ligand; Ad = 1-adamantyl). This paper addresses (1) the spectroscopic and structural characterization of the FeN multiple bond in these interesting three-coordinate iron imido complexes, and (2) the mechanism through which the imido complexes form. The iron(III) imido complexes have been examined by <sup>1</sup>H NMR and electron paramagnetic resonance (EPR) spectroscopies and temperature-dependent magnetic susceptibility (SQUID), and structurally characterized by crystallography and/or extended X-ray absorption fine structure (EXAFS) measurements. These data show that the imido complexes have quartet ground states and short (1.68 ± 0.01 Å) iron−nitrogen bonds. The formation of the imido complexes proceeds through unobserved iron−N<sub>3</sub>R intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an N<sub>3</sub>R radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N<sub>2</sub> loss and imido complex formation. The product distribution between imidoiron(III) products and hexazene-bridged diiron(II) products is solvent-dependent, and the solvent dependence can be explained by coordination of certain solvents to the iron(I) precursor prior to interaction with the organoazide.