The reduction of molecular oxygen by iron porphyrins

Molecular assemblies have been synthesised to reproduce the structure of the cytochrome c oxidase (CcO) active site and to explore the roles played by its different features. It was discovered that a single iron porphyrin, adsorbed at the surface of a graphite electrode, is a selective catalyst for the four-electron reduction of dioxygen to water, at pH 7. To cite this article: D. Ricard et al., C. R. Chimie 5 (2002) 33–36     

Electrocatalytic oxygen reduction by iron tetra-arylporphyrins bearing pendant proton relays

Iron(III) meso-tetra(2-carboxyphenyl)porphine chloride (1) was investigated as a soluble electrocatalyst for the oxygen reduction reaction (ORR) in acetonitrile with [H(DMF)(+)]OTf(-). Rotating ring-disk voltammetry, spectroelectrochemistry, and independent reactions with hydrogen peroxide indicate that 1 has very high selectivity for reduction of O(2) to H(2)O, without forming significant amounts of H(2)O(2). Cyclic voltammetric measurements at high substrate/catalyst ratios (high oxygen pressure) allowed the estimation of a turnover frequency (TOF) of 200 s(-1) at -0.4 V vs Cp(2)Fe(+/0). This is, to our knowledge, the first reported TOF for a soluble ORR electrocatalyst under kinetically controlled conditions. The 4-carboxyphenyl isomer of 1, in which the carboxylic acids point away from the iron center, is a much less selective catalyst. This comparison shows that carboxylate groups positioned to act as proton delivery relays can substantially enhance the selectivity of ORR catalysis.     

Electrocatalytic effect of phenanthroline iron complexes on oxygen reduction in sulfuric acid media

The study of oxygen reduction on a platinum rotating disk was performed at different pHs in 1 M H₂SO₄. An increase in the velocity of this reaction with the addition of 2×10^–3M Fe(II) and 0.1 M 1,10-phenanthroline was observed. This increase depends on the solution pH, i.e. at pH<0.5, it is about 100-fold, whereas for pH>0.5, it is greater than by a factor of 600. This change at pH=0.5 can be explained by a change in the coordination sphere of electrogenerated Fe(II). The complex species Fe(II)–SO₄ at pH<0.5 changes to [Fephen₃]²⁺ at pH>0.5.

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pH 1M H₂SO₄. 2·10^–3M Fe(II) 0,1M 1,10- . pH , pH<0,5 100, pH>0,5 600 . pH=0,5 Fe(II). Fe(II)–SO₄ pH<0,5 [Fephen₃]²⁺ pH>0,5.

     

Electrocatalytic reduction of carbon monoxide on an aluminum electrode modified with iron and manganese

It was found that crystalline inclusions of Fe and Mn in an aluminum matrix catalyze electrochemical reduction of CO in aqueous solutions of 0.1 N H₂SO₄ to C₁-C₃ hydrocarbons.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2201–2203, October, 1989.     

Asymmetric intermolecular cyclopropanation of alkenes by diazoketones catalyzed by Halterman iron porphyrins

The asymmetric addition of diazoacetophenone to styrene derivatives to give optically active cyclopropyl ketones (ee up to 80%) was carried out using chiral iron porphyrins as homogeneous catalysts. Intermolecular N-H functionalization of anilines by means of carbenoid-induced N-H insertion was also possible but without enantioselectivity.     

Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface

Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co(2)(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen.     

Electrocatalytic effect of iron sulfates on oxygen reduction. Influence of the solvation sphere of the mediator

The redox catalysis of oxygen reduction was performed on a platinum rotating disk electrode. The Fe(III)/Fe(II)/H₂SO₄ system at different pH's was used as a MEDIATOR. The catalytic effect of mediator was directly related to the solvation sphere of Fe(III) and Fe(II). Only the redox couple FeHSO ₄ ²⁺ /FeHSO ₄ ⁺ (pH<0) showed a catalytic effect on oxygen reduction.     

The spin distribution in low-spin iron porphyrins

In many low-spin (S = 1/2) iron porphyrin derivatives, electron spin resonance (ESR) spectra indicate that one of the d(pi) orbitals of iron, either a d(xz) or d(yz), depending on the axial ligands of the porphyrin complex as well as their orientation, is essentially singly occupied; the unpaired electron is almost completely located at the metal. In contrast, nuclear magnetic resonance (NMR) and electron nuclear double resonance (ENDOR) spectroscopy convincingly show that a significant share of the unpaired electron is delocalized. This apparent contradiction is explained by the present density-functional-theory (DFT) calculations performed on a heme a model as well as on bis-imidazole-ligated iron porphyrin without substituents. The calculations show that the integrated spin density at the iron atom is nearly one, in agreement with the ESR measurements. However, significant areas with opposite (beta) spin are found along the Fe-N bond axes, thus evoking a need for additional alpha-spin density to be present in the porphyrin ring, ring substituents, and the axial ligands to keep the net amount of unpaired spin exactly one. The gross spin density, that is, the sum of unpaired alpha and beta spins, amounts to about 1.3 electrons. It seems that the degree to which alpha and beta spin dominate in different regions of the heme structure, as evidenced in these calculations, has not been previously observed.     

Electrocatalytic reduction of CO2 to CO by polypyridyl ruthenium complexes

Electrocatalytic reduction of CO(2) by [Ru(tpy)(bpy)(solvent)](2+) (tpy = 2,2':6',2'-terpyridine, bpy = 2,2'-bipyridine) and its structural analogs is initiated by sequential 1e(-) reductions at the tpy and bpy ligands followed by rate limiting CO(2) addition to give a metallocarboxylate intermediate. It undergoes further reduction and loss of CO.     

Enhanced electrocatalytic activity of iron amino porphyrins using a flow cell for reduction of CO2 to CO

The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) in both homogeneous a...     

Quantitative vibrational dynamics of iron in nitrosyl porphyrins

We use quantitative experimental and theoretical approaches to characterize the vibrational dynamics of the Fe atom in porphyrins designed to model heme protein active sites. Nuclear resonance vibrational spectroscopy (NRVS) yields frequencies, amplitudes, and directions for 57Fe vibrations in a series of ferrous nitrosyl porphyrins, which provide a benchmark for evaluation of quantum chemical vibrational calculations. Detailed normal mode predictions result from DFT calculations on ferrous nitrosyl tetraphenylporphyrin Fe(TPP)(NO), its cation [Fe(TPP)(NO)]+, and ferrous nitrosyl porphine Fe(P)(NO). Differing functionals lead to significant variability in the predicted Fe-NO bond length and frequency for Fe(TPP)(NO). Otherwise, quantitative comparison of calculated and measured Fe dynamics on an absolute scale reveals good overall agreement, suggesting that DFT calculations provide a reliable guide to the character of observed Fe vibrational modes. These include a series of modes involving Fe motion in the plane of the porphyrin, which are rarely identified using infrared and Raman spectroscopies. The NO binding geometry breaks the four-fold symmetry of the Fe environment, and the resulting frequency splittings of the in-plane modes predicted for Fe(TPP)(NO) agree with observations. In contrast to expectations of a simple three-body model, mode energy remains localized on the FeNO fragment for only two modes, an N-O stretch and a mode with mixed Fe-NO stretch and FeNO bend character. Bending of the FeNO unit also contributes to several of the in-plane modes, but no primary FeNO bending mode is identified for Fe(TPP)(NO). Vibrations associated with hindered rotation of the NO and heme doming are predicted at low frequencies, where Fe motion perpendicular to the heme is identified experimentally at 73 and 128 cm-1. Identification of the latter two modes is a crucial first step toward quantifying the reactive energetics of Fe porphyrins and heme proteins.     

Electrocatalytic reduction of polyhydric alcohols to hydrocarbons

A study was carried out on the electrochemical reduction of polyhydric alcohols using an iron-coated titanium cathode. The mechanism of this reaction was discussed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1697–1699, July, 1991.     

Production of iron phosphide by reduction of polyphosphates with metallic iron

A composition of the products of interaction in the system (NaPO₃)₃-Fe under heating was studied by X-ray analysis and calculation of ΔG _T ^○ . Possible pathways of the formation of iron phosphides of different chemical composition and other co-products during heating of sodium and iron cyclotriphophate to 1000°C were described on the basis of thermodynamic and X-ray data. The conditions for obtaining individual types of iron phosphides Fe₃P, Fe₂P, and FeP by interaction of sodium cyclotriphophate with metallic iron under heating were found.     

Computational investigation of the concerted dismutation of chlorite ion by water-soluble iron porphyrins

A detailed density functional theory examination of the reaction of an iron porphyrin chlorite dismutase model complex with chlorite was performed. We find that the molecular oxygen production observed occurs via the formation of η(1)-Fe(III) chlorite species, followed by the formation of O═Fe(IV) (compound II) and chlorine monoxide through homolytic bond cleavage. Chlorine monoxide then rebounds to form Fe(III)-peroxyhypochlorite followed by subsequent loss of chloride and loss of dioxygen accompanied by spin conversion to produce the Fe(III) complex and complete the catalytic cycle.