Kinetic studies of reactions of iron(IV)-oxo porphyrin radical cations with organic reductants

Enhanced iron(III) corrole-catalyzed oxidations with iodobenzene diacetate: Synthetic and mechanistic investigations

“…Hammett + substituent constant. The slope ( + ) of the plot is-0.79, again, which is similar to the values found with model Compound I species with a strong binding chloride counterion ( + = -0.89) [33]. However, this observed + value is about 2-fold larger in magnitude than the previously reported value (−0.28) found for a related chloroperoxidase (CPO) Compound I [35].…”

“…Notably, the competitive catalytic oxidation of PhEt-d 0 and PhEtd 10 revealed a kinetic isotope effect (KIE) of k H /k D = 4.40 ± 0.21 at 298 K, similar to the KIE reported for the same reaction with an electron-deficient iron(IV)-oxo porphyrin radical cation species (model Compound I). [33] The observed KIE is larger than those observed in autooxidation processes (typical KIE = 1-2), [34] supporting a non-radical mechanism. ; material balances > 95%.…”

Activation of the cytochrome c peroxidase of Pseudomonas aeruginosa. The role of a heme-linked protein loop: A mutagenesis studies

“…The H71G form of the protein presents an absorption spectrum which has previously been associated with the formation of an oxy-ferryl heme centre coupled to an adjacent Trp radical in a number of peroxidase systems [26][27][28][29]. The loop mutant produces a Soret spectrum for the product of reaction with hydrogen peroxide typical of an oxy-ferryl heme centre coupled to a porphyrin cation radical previously observed in a number of other peroxidase proteins [30][31][32][33]. EPR spectroscopy confirms the presence of radical species in these mutant peroxide treated proteins (Fig.…”

Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes

“…Excellent reviews on the reactivity of iron-oxo porphyrin complexes can be found in the literature, including those from Fujii (2000, 21 2002 22 , 2016 23 ) Meunier et al (2004), 24 Groves (2006), 25 Newcomb (2006), 26 Nam (2007), 27 Costas (2011), 28 Ray and Meyer (2012), 29 and Rutkowska-Zbik (2014) 30 . Dedicated chapters in The Porphyrin Handbook (2000), 18,31-34 Handbook of Porphyrin Science, 35 and other compilations 36-38 can also be found.…”