93085-17-7Relevant academic research and scientific papers
Effect of imidazole and phenolate axial ligands on the electronic structure and reactivity of oxoiron(IV) porphyrin π-cation radical complexes: Drastic increase in oxo-transfer and hydrogen abstraction reactivities
Takahashi, Akihiro,Kurahashi, Takuya,Fujii, Hiroshi
, p. 2614 - 2625 (2009/07/30)
To study the effect of axial ligands on the electronic structure and reactivity of compound I of peroxidases and catalases, oxoiron(IV) porphyrin π-cation radical complexes with imidazole, 2-methylimidazole, 4(5)-methylimidazole, and 3-fluoro-4-nitropheno
Detection of Alkylperoxo and Ferryl, (Fe(IV)=O)(2+), Intermediates during the Reaction of tert-Butyl Hydroperoxide with Iron Porphyrins in Toluene Solution
Arasasingham, Ramesh D.,Cornman, Charles R.,Balch, Alan L.
, p. 7800 - 7805 (2007/10/02)
PFeII and PFeIIIOH (P is a porphyrin dianion) catalyze the decomposition of tert-butyl hydroperoxide in toluene solution without appreciable attack on the porphyrin ligand. (1)H NMR spectroscopic studies at low temperature (-70 deg C) give evidence for the formation of a high-spin, five-coordinate intermediate, PFeIIIOOC(CH3)3.On warming this decomposes to PFeIIIOH (P = tetramesitylporphyrin, TMP) or PFeIIIOFeIIIP (P = tetra-p-tolylporphyrin, TTP) with the formation of (TMP)FeIV=O as an observed intermediate in the first case.Treatment of PFeIIIOOC(CH3)3 at -70 deg C with N-methylimidazole (MeIm) yields the intermediate (MeIm)PFeIV=O.Organic products formed from this reaction are tert-butyl alcohol, di-tert-butyl peroxide, benzaldehyde, acetone, and benzyl-tert-butyl peroxide, which arise largely from a radical chain process initiated by the iron porphyrin but continuing without its intervention.
Oxygenation Patterns for Iron(II) Porphyrins. Peroxo and Ferryl (FeIVO) Intermediates Detected by 1H Nuclear Magnetic Resonance Spectroscopy during the Oxygenation of (Tetramesitylporphyrin)iron(II)
Balch, Alan L.,Chan, Yee-Wai,Cheng, Ru-Jen,Mar, Gerd N. La,Latos-Grazynski, Lechoslaw,Renner, Mark W.
, p. 7779 - 7785 (2007/10/02)
The reaction between unligated (tetramesitylporphyrin)iron(II) (TMPFeII) and dioxygen in a toluene solution has been examined by 1H NMR spectroscopy.At -70 deg C, TMPFeII reacts with O2 to yield TMPFeIIIOOFeIIITMP that has spectroscopic properties similar to those of other peroxo-bridged complexes.On warming, TMPFeIIIOOFeIIITMP decomposes to yield a second intermediate (identified as TMPFeIVO) and TMPFeIIIOH, the final, stable product.TMPFeIIIOOFeIIITMP reacts with N-methylimidazole (N-MeIm) to produce (N-MeIm)TMPFeO2 and (N-MeIm)2TMPFeII.The former has been independently prepared from (N-MeIm)2TMPFeII and dioxygen at -50 deg C. TMPFeIVO reacts with N-MeIm to form (N-MeIm)TMPFeIVO that has been identified by comparison with other FeIVO complexes.TMPFeIVO reacts with triphenylphosphine at -50 deg C to yield triphenylphosphine oxide while TMPFeIIIOOFeIIITMP is unreactive toward triphenylphosphine under these conditions.TMPFeII is a catalyst for the oxidation of triphenylphosphine by dioxygen. 1H NMR spectra and resonance assignments for each species are described.
