Metalloporphyrins oxidation

The next important information on the product is derived from the electronic absorption spectrum. This can usually be obtained by electrolysis of a dilute solution of the metalloporphyrin at a constant potential or by oxidometric titrations directly in the absorption cell. Most redox reactions with metalloporphyrins give good isosbestic points when absorption spectra are taken at various stages of oxidation, and they are fully reversible when no chemical addition reaction to the porphyrin ligand has occurred. Ten typical absorption spectra of metalloporphyrins are given below and correlated with the various metalloporphyrin oxidation states. 

The high stability of porphyrins and metalloporphyrins is based on their aromaticity, so that porphyrins are not only most widespread in biological systems but also are found as geoporphyrins in sediments and have even been detected in interstellar space. The stability of the porphyrin ring system can be demonstrated by treatment with strong acids, which leave the macrocycle untouched. The instability of porphyrins occurs in reduction and oxidation reactions especially in the presence of light. The most common chemical reactivity of the porphyrin nucleus is electrophilic substitution which is typical for aromatic compounds. 

The oxidation states and reversible redox reactions of metalloporphyrins. J. H. Furhrhop, Struct. Bonding (Berlin), 1974,18,1-67 (221). 

Metalloporphyrins as catalysts of chain transfer in radical polymerisation and stereoselective oxidation. L. Karmilova, G. V. Ponomarev, B. R. Smirnov and I. M. Bel yovskii, Russ. Chem. Rev. (Engl. Transl), 1984, 53,132 (44). 

Catalysis by metalloporphyrins of reactions involving oxidation by molecular oxygen and oxygen-containing compounds. N. S. Enikolopyan, K. A. Bogdanova, L. V. Karmilova and K. A. Askarov, Russ. Chem. Rev. (Engl. Transl.), 1985,54,215 (188). 

It was shown that dibenzothiophene oxide 17 is inert to 1-benzyl-l,4-dihydro nicotinamide (BNAH) but that, in the presence of catalytic amounts of metalloporphyrin, 17 is reduced quantitatively by BNAH. From experimental results with different catalysts [meso-tetraphenylporphinato iron(III) chloride (TPPFeCl) being the best] and a series of substituted sulfoxides, Oae and coworkers80 suggest an initial SET from BNAH to Fe1 followed by a second SET from the catalyst to the sulfoxide. The results are also consistent with an initial coordination of the substrate to Fem, thus weakening the sulfur-oxygen bond in a way reminiscent of the reduction of sulfoxides with sodium borohydride in the presence of catalytic amounts of cobalt chloride81. 

Akiba investigated the electrochemical behavior of a variety of phosphorus octaethylporphyrin derivatives all compounds showing a single reversible oxidation wave [91]. The absolute difference in potential between the first ring-centered oxidation and reduction varies from 2.19 to 2.36 V in dichloromethane. These values are within the range of the HOMO-LUMO gap observed for most metalloporphyrins. 

One-electron oxidation of the vinylidene complex transforms it from an Fe=C axially symmetric Fe(ll) carbene to an Fe(lll) complex where the vinylidene carbon bridges between iron and a pyrrole nitrogen. Cobalt and nickel porphyrin carbene complexes adopt this latter structure, with the carbene fragment formally inserted into the metal-nitrogen bond. The difference between the two types of metalloporphyrin carbene, and the conversion of one type to the other by oxidation in the case of iron, has been considered in a theoretical study. The comparison is especially interesting for the iron(ll) and cobalt(lll) carbene complexes Fe(Por)CR2 and Co(Por)(CR2) which both contain metal centers yet adopt... 

Sheldon RA (1994) Metalloporphyrins in catalytic oxidations. Marcel Dekker, New York... 

In the second oxidation method, a metalloporphyrin was used to catalyze the carotenoid oxidation by molecular oxygen. Our focus was on the experimental modeling of the eccentric cleavage of carotenoids. We used ruthenium porphyrins as models of cytochrome P450 enzymes for the oxidation studies on lycopene and P-carotene. Ruthenium tetraphenylporphyrin catalyzed lycopene oxidation by molecular oxygen, producing (Z)-isomers, epoxides, apo-lycopenals, and apo-lycopenones. 

Of considerable interest was the demonstration that metalloporphyrins and the like can be used as nonmetallic catalysts in electrochemical reactions, nourishing hopes that in the future, expensive platinum catalysts could be replaced. Starting in 1968, dimensionally stable electrodes with a catalyst prepared from the mixed oxides of titanium and ruthenium found widespread use in the chlorine industry. 

Fuhrhop, J.-H. The Oxidation States and Reversible Redox Reactions of Metalloporphyrins. Vol. 18, pp. 1-67. 

As a result of strong electronic interactions between the two metalloporphyrin units, there is a substantial uncertainty in assigning oxidation states in mixed-valence group 2 complexes of redox-active metals, such as Co. Thus, although reduced neutral C02 derivatives can be reasonably well described as those of Co the location (metal versus porphyrin) of the electron hole(s) in the singly and doubly oxidized derivatives is not known definitively, and may be very sensitive to the medium [LeMest et al., 1996, 1997]. For example, in benzonitrile, the UV-vis spectmm of [(FTF4)Co2]" ... 

These metalloporphyrins are unique among Fe and Co porphyrins in their high catalytic efficiency of electroreduction of H2O2 (at potentials <0.75 V vs. NHE at pH 7), as well as disproportionation and oxidation of H2O2 (at potentials >0.8 V). 

Only three steps of the proposed mechanism (Fig. 18.20) could not be carried out individually under stoichiometric conditions. At pH 7 and the potential-dependent part of the catalytic wave (>150 mV vs. NHE), the —30 mV/pH dependence of the turnover frequency was observed for both Ee/Cu and Cu-free (Fe-only) forms of catalysts 2, and therefore it requires two reversible electron transfer steps prior to the turnover-determining step (TDS) and one proton transfer step either prior to the TDS or as the TDS. Under these conditions, the resting state of the catalyst was determined to be ferric-aqua/Cu which was in a rapid equilibrium with the fully reduced ferrous-aqua/Cu form (the Fe - and potentials were measured to be within < 20 mV of each other, as they are in cytochrome c oxidase, resulting in a two-electron redox equilibrium). This first redox equilibrium is biased toward the catalytically inactive fully oxidized state at potentials >0.1 V, and therefore it controls the molar fraction of the catalytically active metalloporphyrin. The fully reduced ferrous-aqua/Cu form is also in a rapid equilibrium with the catalytically active 5-coordinate ferrous porphyrin. As a result of these two equilibria, at 150 mV (vs. NHE), only <0.1%... 

The chemically catalyzed oxidation of carotenoids by metalloporphyrins has also been described in the literature. In 2000, French et al. described a central cleavage mimic system (ruthenium porphyrin linked to cyclodextrins) that exhibited a 15,1 S -regiosclectivity of about 40% in the oxidative cleavage of [3-carotene by tert-butyl hydroperoxide in a biphasic system (French et al. 2000). 

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