Reactivity of Hydroperoxide Bound to a Mononuclear Non-Heme Iron Site

Citations Over TimeTop 10% of 2002 papers

Abstract

The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H(2)bppa)(OOH)](2+) (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H(2)bppa)(HCOO)](ClO(4))(2) with H(2)O(2) in acetone at -50 degrees C gave characteristic UV-vis (lambda(max) = 568 nm, epsilon = 1200 M(-1) cm(-1)), ESR (g = 7.54, 5.78, and 4.25, S = (5)/(2)), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)](2+)), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d(6)-acetone revealed two intense bands at 621 and 830 cm(-1), which shifted to 599 and 813 cm(-1), respectively, when reacted with (18)O-labeled H(2)O(2). Reactions of the isolated (bppa)Fe(III)-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H(2)bppa)Fe(III)-O*].

Related Papers

• → Kinetic Study on the Reactivity of Azanone (HNO) toward Cyclic C-Nucleophiles(2021)9 cited
• → Non‐Aromatic 3H‐Pyrroles in the Reaction with Nucleophiles: Is High Reactivity a Myth?(2019)7 cited
• → Reactivity of Anionic Pentacoordinated Silicon Complexes towards Nucleophiles(1986)48 cited
• → Enhancement of the High-Field J c properties of MgB2/Fe Tapes by Acetone Doping(2009)3 cited
• → Transition Metal‐Catalyzed Cycloisomerizations of Allenes(2004)12 cited