Three-coordinate terminal imidoiron(III) complexes: structure, spectroscopy, and mechanism of formation.
Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFe=NAd (L = bulky beta-diketiminate ligand; Ad = 1-adamantyl). This paper addresses (1) the spectroscopic and structural characterization of the Fe=N 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 (1)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 A) iron-nitrogen bonds. The formation of the imido complexes proceeds through unobserved iron-N(3)R intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an N(3)R radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N(2) 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.
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Ryan E
RE
Cowley
Nathan J
NJ
DeYonker
Nathan A
NA
Eckert
Thomas R
TR
Cundari
Serena
S
DeBeer
Eckhard
E
Bill
Xavier
X
Ottenwaelder
Christine
C
Flaschenriem
Patrick L
PL
Holland
D001386:Azides / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007094:Imides / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D056928:X-Ray Absorption Spectroscopy
D001386:Azides; D005290:Ferric Compounds; D007094:Imides; D009942:Organometallic Compounds