Oxidation of Chloride and Subsequent Chlorination of Organic Compounds by Oxoiron(IV) Porphyrin π‐Cation Radicals

Cong, Zhiqi; Kurahashi, Takuya; Fujii, Hiroshi

doi:10.1002/ange.201104461

Cited by 14 publications

(1 citation statement)

References 57 publications

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“…[11,12] In homogeneous catalysis, the oxidation of Cl À by metal-oxo complexes is of importance for understanding the mechanism of halide oxidation by enzymes such as haloperoxidases and cytochrome P450; previous examples in this area include the oxidation of Cl À by an (oxo)manganese porphyrin complex to give hypochlorite [13] and by (oxo)iron porphyrins to give chlorination products. [14] Recently, a considerable number of DFT calculations on Cl À oxidation to Cl 2 by using heterogeneous metal catalysts have been reported. [11a] Complex 1 is an interesting example of a highly oxidizing metal-oxo complex that has been isolated and reported to oxidize HCl (or NaCl) to Cl 2 within minutes at room temperature.…”

Section: Oxidation Of Hydrochloric Acidmentioning

confidence: 99%

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

Guan

Chan

Che

2013

Chemistry An Asian Journal

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The electronic structure and redox properties of the highly oxidizing, isolable Ru(V)=O complex [Ru(V)(N4O)(O)](2+), its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol(-1), respectively. The overall free energy activation barrier (ΔG(≠)=25.5 kcal mol(-1)) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru(III)(N4O)(HOCl)](2+) (ΔG=15.0 kcal mol(-1)) and the substitution of HOCl by a water molecule (ΔG(≠)=10.5 kcal mol(-1)). For water oxidation, nucleophilic attack on Ru(V)=O by water, leading to O-O bond formation, has a free energy barrier of 24.0 kcal mol(-1), the major component of which comes from the cleavage of the H-OH bond of water. Intermolecular self-coupling of two molecules of [Ru(V)(N4O)(O)](2+) leads to the [(N4O)Ru(IV)-O2-Ru(III)(N4O)](4+) complex with a calculated free energy barrier of 12.0 kcal mol(-1).

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Section: Oxidation Of Hydrochloric Acidmentioning

confidence: 99%

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

Guan

Chan

Che

2013

Chemistry An Asian Journal

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Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations

et al. 2013

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The oxidation of light alkanes that is catalyzed by heme and nonheme iron enzymes is widely proposed to involve highly reactive {Fe V = O} species or {Fe IV = O} ligand cation radicals. The identification of these high-valent iron species and the development of an iron-catalyzed oxidation of light alkanes under mild conditions are of vital importance. Herein, a combination of tridentate and bidentate ligands was used for the generation of highly reactive nonheme {Fe=O} species. A method that employs [Fe III (Me 3 tacn)(Cl-acac)Cl] + as a catalyst in the presence of oxone was developed for the oxidation of hydrocarbons, including cyclohexane, propane, and ethane (Me 3 tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane; Cl-acac = 3-chloro-acetylacetonate). The complex [Fe III (Tp) 2 ] + and oxone enabled stoichiometric oxidation of propane and ethane. ESI-MS, EPR and UV/Vis spectroscopy, 18 O labeling experiments, and DFT studies point to [Fe IV (Me 3 tacn)({Cl-acac}C + )(O)] 2+ as the catalytically active species.

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A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four‐Electron Oxidation Product

2015

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Thee thene-bridged cobalt(II) porphyrin dimers trans-1 and cis-1 (Scheme 1) were synthesized in excellent yield by heating the corresponding free ligand with Co(OAc) 2 (added as as olution in methanol) in CH 2 Cl 2 at reflux under N 2 .T he dissolution of trans-1 into THF resulted in the formation of the five-coordinate complex trans-2·THF,w hich was isolated Scheme 1. Synthesis of the complexes.

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Oxidation of Chloride and Subsequent Chlorination of Organic Compounds by Oxoiron(IV) Porphyrin π‐Cation Radicals

Cited by 14 publications

References 57 publications

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations

A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four‐Electron Oxidation Product

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Oxidation of Chloride and Subsequent Chlorination of Organic Compounds by Oxoiron(IV) Porphyrin π‐Cation Radicals

Cited by 14 publications

References 57 publications

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations

A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four‐Electron Oxidation Product

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A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [Ru^V(N₄O)(O)]²⁺: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations