113533-07-6

Upstream product

• 98715-91-4 hydroxo(5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)iron(III) 
• 113859-72-6 {tetrakis(2,6-dichlorophenyl)porphinato}iron(III) perchlorate 
• 91042-27-2 5,10,15,20-tetra(2',6'-dichlorophenyl)porphyrinatoiron(III) chloride 
• 937-14-4 3-chloro-benzenecarboperoxoic acid 
• 3240-34-4 [bis(acetoxy)iodo]benzene 

Downstream Products

• 98715-91-4 hydroxo(5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)iron(III) 
• 146082-00-0 (m-chlorobenzoate)iron(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin 

Relevant academic research and scientific papers

Kinetics and mechanism of oxidation reactions of porphyrin-iron(IV)-oxo intermediates

The kinetics of the reactions of three porphyrin-iron(IV)-oxo derivatives with alkenes and benzylic alcohols were measured. The iron-oxo systems studied were 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (2a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (2b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-iron(IV)-oxo (2c). Species 2 were stable for hours at room temperature as dilute solutions in acetonitrile and reacted hundreds to thousands of times faster in the presence of high concentrations of substrates. Typical second-order rate constants determined from pseudo-first-order kinetic studies are 1-2 × 10-2 M -1 s-1 for reactions with styrene and 3 × 10 -2 M-1 s-1 for reactions with benzyl alcohol. The reactivity order for the iron-oxo species was 2a > 2b > 2c, which is inverted from that expected on the basis of the electron demand of the porphyrin macrocycles, and the oxidation reaction was suppressed when excess porphyrin-iron(lll) complex was added to reaction mixtures. These observations indicate that the reactions involve disproportionation of the iron(IV)-oxo species 2 to give an iron(III) species and a more highly oxidized iron species, presumed to be an iron(IV)-oxo porphyrin radical cation, that is the true oxidant in the reactions. Analyses of the kinetics of oxidations of a series of para-substituted benzylic alcohols with Hammett σ--substituent constants and with a dual-parameter method developed by Jiang (Jiang, X. K. Acc. Chem. Res. 1997, 30, 283) indicated that considerable positive charge developed on the benzylic carbons in the oxidation reactions, as expected for electrophilic oxidants, and also that substantial radical character developed on the benzyl carbon in the transition states.

Insights from kinetic studies of photo-generated compound II models: Reactivity toward aryl sulfides

Iron(IV)-oxo porphyrins [FeIV(Por)O] (Por = poprhyrin), commonly called compound II models, were produced in three electron-deficient ligands by visible light irradiation of highly photo-labile porphyrin-iron(III) bromates or chlorates. The kinetics of oxygen transfer atom (OAT) reactions with aryl sulfides by these photo-generated [FeIV(Por)O] (3) were studied in CH3CN solutions. The iron(IV)-oxo porphyrins under study include 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (3b), and 5,10,15,20-tetra(pentafluorophenyl)porphyrin-iron(IV)-oxo (3c). As expected, complexes 3 were competent oxidants and reacted rapidly with thioanisoles to give the corresponding sulfoxides with minor over-oxidation sulfones. Apparent second-order rate constants determined under pseudo-first-order conditions for sulfide oxidation reactions are (9.8 ± 0.1) × 102–(3.7 ± 0.3) × 101 M?1 s?1, which are 3 to 4 orders of magnitude greater in comparison to those of alkene epoxidations and activated C–H bond oxidations by the same oxo species. Conventional Hammett analyses gave non-linear correlations, indicating no significant charge developed at the sulfur during the oxidation process. For a given substrate, the reactivity order for the iron(IV)-oxo species was 3c 3b 3a, which is inverted from expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. The absolute rate constants from kinetic studies provided insights into the transient oxidants in catalytic reactions under turnover conditions where actual reactive intermediates are not observable. Our kinetic and catalytic competition results strongly suggest that 3 may undergo a disproportionation reaction to form a higher oxidized iron(IV)-oxo porphyrin radical cations as the true oxidant.

Critical factors in determining the heterolytic versus homolytic bond cleavage of terminal oxidants by Iron(III) porphyrin complexes

Heterolytic versus homolytic cleavage of the metal-bound terminal oxidant is the key for determining the nature of reactive intermediates in metalloenzymes and metal catalyzed oxygenation reactions. Here, we study the bond cleavage process of hypochlorite

An investigation of ligand effects on the visible light-induced formation of porphyrin-iron(iv)-oxo intermediates

High-valent porphyrin-iron-oxo intermediates are the central oxidizing species in heme-containing enzymes and synthetic oxidation catalysts. In this work, we investigated a new photochemical entry to porphyrin-iron(iv)-oxo derivatives in a variety of porp

Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations

Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed f

Hydrogen atom abstraction and hydride transfer reactions by iron(IV)-oxo porphyrins

(Chemical Equation Presented) True identity revealed: The C-H bond activation of alkyl aromatics by synthetic iron(IV)-oxo porphyrin species and the hydride transfer of NADH analogues to them occur through H-atom abstraction and proton-coupled electron-transfer mechanisms, respectively. Mechanistic studies revealed that iron(IV)-oxo porphyrin π, not iron(IV)-oxo porphyrin pradical cations, are the true oxidant.

Formation, Characterization, and Reactivity of the Oxene Adduct of iron(III) Perchlorate in Acetonitrile. Model for the Reactive Intermediate of Cytochrome P-450

Combination of iron(III) perchlorate with pentafluoroiodosobenzene, m-chloroperbenzoic acid, or ozone in acetonitrile at -35 deg C yields a green porphyrin-oxene adduct.This species, which has been characterized by spectroscopic, magnetic, and electrochemical methods, cleanly and stereospecifically epoxidizes olefins (>99percent exo-norbornene oxide).The reaction chemistry and electronic characterization of the adduct are consistent with an oxygen atom covalently bound to an iron(II)-porphyrin radical center (Por.-)FeII(O)+>.The latter has the spectral, magnetic, and redox characteristics of compound I of horseradish peroxidase (HRP) and the selective stereospecific oxygenase character of the reactive intermediate for cytochrome P-450.Reduction of the green species by one electron equivalent yields a red species, PorFeII(O), which has the spectral characteristics and reactivity of compound II of HRP.The iron(III)-porphyrin is an efficient catalyst for (a) the stereospecific epoxidation of olefins and (b) the oxidative cleavage of α-diols by F5PhIO and m-ClPhC(O)OOH; with H2O2, there is extensive attack on the porphyrin ring and no significant reaction with olefins or α-diols.