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 1H 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−N3R intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an N3R radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N2 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.