243458-48-2

Upstream product

• 7722-84-1 dihydrogen peroxide 
• 312321-65-6 [Fe(II)(N-benzyl-N,N',N'-tris(2-pyridylmethyl)-1,2-diaminoethane)]⁽²⁺⁾ 
• 80937-33-3 oxygen 
• 316381-49-4 N¹-benzyl-N¹,N²,N²-tris(pyridine-2-ylmethyl)ethane-1,2-diamine 

Downstream Products

• 423720-03-0 [Fe(N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine)(η2-OO)](1+) 

Relevant academic research and scientific papers

Dioxygen activation by mononuclear nonheme iron(II) complexes generates iron-oxygen intermediates in the presence of an NADH analogue and proton

(Chemical Equation Presented) One primary goal in biomimetic research is to understand mechanisms of dioxygen activation, structures of reactive intermediates, and reactivities of the intermediates involved in catalytic oxidation reactions by metalloenzym

Reactivities of mononuclear non-heme iron intermediates including evidence that iron(III) hydroperoxo species is a sluggish oxidant

There is an intriguing, current controversy on the involvement of iron(III)-hydroperoxo species as a second electrophilic oxidant in oxygenation reactions by heme and non-heme iron enzymes and their model compounds. In the present work, we have performed reactivity studies of the iron-hydroperoxo species in nucleophilic and electrophilic reactions, with in situ-generated mononuclear non-heme iron(III)-hydroperoxo complexes that have been well characterized with various spectroscopic techniques. The intermediates did not show any reactivities in the nucleophilic (e.g., aldehyde deformylation) and electrophilic (e.g., oxidation of sulfide and olefin) reactions. These results demonstrate that non-heme iron(III)-hydroperoxo species are sluggish oxidants and that the oxidizing power of the intermediates cannot compete with that of high-valent iron(IV)-oxo complexes. We have also reported reactivities of mononuclear non-heme iron(III)-peroxo and iron(IV)-oxo complexes in the aldehyde deformylation and the oxidation of sulfides, respectively.

Mononuclear non-heme iron(III) peroxide complexes: Syntheses, characterisation, mass spectrometric and kinetic studies

A series of transient interconvertible protonated and deprotonated mononuclear Fe(III) peroxo species are derived from the pH dependent reaction of dihydrogen peroxide with mononuclear iron(II) or iron(III) complexes of general formulation [Fe(Rtpen)X](A)n, n = 1,2; X = Cl,Br; Rtpen = N-alkyl-N,N′,N′-tris(2-pyridylmethyl)ethane-1,2-diamine, alkyl = R = CH3CH2, CH3CH2CH2, HOCH2CH2, (CH3)2CH, C6H5, and C6H5CH2; A = ClO4, PF6. The low-spin iron(III) hydroperoxide complex ions [Fe(Rtpen)(η1-OOH)]2+ are purple chromophores and the high-spin iron(III) peroxide complexes, [Fe(Rtpen)(η2-OO)]+ are blue chromophores. The spectroscopic observation (ESR, UV-vis, ESI MS) of a low-spin iron(III) precursor species [Fe(Rtpen)(η1-OCH3)]2+ and kinetic studies show that formation of [Fe(Rtpen)(η1-OOH)]2+ from iron(II) solution species is a two step process. The first step, the oxidation of the iron(II) complex to [Fe(Rtpen)(OCH3)]2+, is faster than the subsequent ligand substitution during which [Fe(Rtpen)(eta;1-OOH)]2+ is formed. The kinetic data are consistent with an interchange associative mechanism for the ligand substitution, and a role for the proton bound to the uncoordinated hydroperoxide oxygen atom is suggested. The stability of [Fe(Rtpen)(η1-OOH)]2+ R = HOCH2CH2, is significantly lower than for the peroxide complexes generated from the other alkyl substituted ligands (t1/2 ca. 10 min vs. several hours). Tandem MS/MS experiments with the [Fe(Rtpen)(η1-OOH)]2+ ions show fragmentation via O-O cleavage to give the novel ferryl species [Fe(Rtpen)(O)]2+. By contrast the [Fe(Rtpen)(η2-OO)]+ ions are stable under the same gas phase conditions. This indicates a weaker O-O bond in the Fe(III) hydroperoxide complex ions, and that [FeIIIOOH]2+ rather than [FeIIIOO]+ species are the precursors to, at least, the ferryl FeIV=O species. Crystal structures of four starting iron(II) compounds, [Fe(Rtpen)Cl]PF6, R = HOCH2CH2, CH3CH2CH2, C6H5CH2, and [Fe(bztpen)Br]PF6 show the iron atoms in distorted octahedral geometries with pentadentate Rtpen coordination with the halide ion as the sixth ligand. The structure of [Fe(etOHtpen)Cl]PF6 shows an intermolecular H-bonding interaction between the dangling hydroxyethyl group and the chloride of a neighbouring molecule with O-H...Cl, 3.219(2) A.