Summary
The synthesis and characterization are reported for (μ-nitrido)bis[(octaphenyltetraazaporphyrinato)iron] ([OPTAP)Fe]2N). The [(OPTAP)Fe]2N dimer is paramagnetic with one unpaired electron per dimer unit and shows a typical axially symmetric e.p.r. spectrum in non-polar solvents at liquid N2 temperature (g⊥=2.126, g‖=2.001), with well-resolved superhyper-fine splitting resulting from the μ-nitrido bridge (A N⊥ =2.48mT, A N‖ =2.60mT).
A pyridine monoadduct of [(OPTAP)Fe]2N, formed in frozen glasses has been characterised by changes in e.p.r. spectra. Electronic spectra show no pyridine adduct formation at 298 K. Mössbauer parameters (IS=−0.042 mm/s, QS=1.769mm/s at 298K) are indicative of the predominant iron(IV) character in [(OPTAP)Fe]2N.
The pyridine monoadduct binds O2 reversibly. The O2 adduct was characterized by e.p.r. spectroscopy (g1=2.062, g2=2.007, g3=2.000). O2 titration as monitored by e.p.r. shows that the adduct stoichiometry is one O2 per dimer. A spin-pairing model for O2 binding accounts for the observed O2-[(OPTAP)Fe]2N interaction.
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Stuzhin, P.A., Latos-Grażyński, L. & Jezierski, A. Synthesis and properties of binuclear nitride-bridged iron octaphenyltetraazaporphyrin. E.p.r. studies of dioxygen adduct formation. Transition Met Chem 14, 341–346 (1989). https://doi.org/10.1007/BF01032506
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DOI: https://doi.org/10.1007/BF01032506