Metalloporphyrin/Iodine(III)‐Cocatalyzed Oxygenation of Aromatic Hydrocarbons

Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrin‐mediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5–20 mol% of iodobenzene and 5 mol% of a water‐soluble iron(III)‐porphyrin complex. 2‐tert‐Butylanthracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10‐dihydroanthracene, 1,2,3,4‐tetrahydronaphthalene, and 2,3‐dihydro‐1H‐indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)‐porphyrin to the oxoiron(IV)‐porphyrin cation‐radical complex by the intermediate iodine(III) species. The oxoiron(IV)‐porphyrin cation‐radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.     

The road to non-heme oxoferryls and beyond

Oxoiron(IV) species are often implicated in the catalytic cycles of oxygen-activating non-heme iron enzymes. The paucity of suitable model complexes stimulated us to fill this void, and our synthetic efforts have afforded a number of oxoiron(IV) complexes. This Account provides a chronological perspective of the observations that contributed to the generation of the first non-heme iron(IV)-oxo complexes in high yield and summarizes their salient properties to date.     

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 for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3 ± 0.2) × 10(2) M(-1) s(-1). The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.     

Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins

The oxidation of chloro-5-10,15,20-tetramesitylporphyrinotoiron(III) with peroxyacids affords a reactive oxoiron(IV)-porphyrin cation radical species 2. The characterization of 2 and its oxochromium analogs 3, 4 and 5 are reviewed. The nature of reactive oxochromium species derived from chromyl reagents is also reviewed. The oxidation of triphenylphosphine by CrOTPP (11), CrOTTP (13) and CrOTMP (14) is described. Variations in the rate constants indicate that steric factors affect the rate of oxygen atom transfer. Activation parameters for the oxidation of triphenylphosphine by 14 are ΔH^≠ = 6.96 kcal/mol and ΔS^≠ = −39 eu. The oxidation of t-butylphenylcarbinol (18) by CrOTPP gave predominantly benzaldehyde via carbon—carbon bond cleavage while the chromium(III) porphyrin-catalyzed oxidation of 18 by iodosylbenzene afforded t-butylphenylketone.     

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.     

Remarkable effect of the preparation method on the state of vanadium in BEA zeolite: Lattice and extra-lattice V species

The state of vanadium in two BEA zeolites is investigated by XRD, FTIR, DR UV–vis and EPR. One of the samples, VAlBEA (1.3 wt.% of V), is prepared by conventional ion exchange and the other, VSiBEA (2.0 wt.% of V), by a two-step postsynthesis method involving dealuminated BEA zeolite. No structural changes are observed after incorporation of vanadium into AlBEA zeolite by ion-exchange method. In contrast, the impregnation of SiBEA with V(IV) (VOSO₄) precursor leads to an increase of unit cell parameters of the BEA, to the consumption of silanol groups in vacant T-sites and incorporation of V in the framework of BEA zeolite as well dispersed tetrahedral V(V) species. NO and CO used as IR probe molecules, DR UV–vis and EPR allow to establish the oxidation state of vanadium in as prepared, oxidized, activated and reduced VAlBEA and VSiBEA zeolites. The IR spectra of oxidized, activated and reduced VAlBEA samples are very similar. It suggests that V introduced by ion exchange in extra-lattice position is stabilized on all samples in similar oxidation state. CO adsorption evidence the presence of vanadium in IV oxidation state via IR bands at about 2200 and 2180 cm⁻¹ assigned to V(IV)–CO monocarbonyl and V(IV)–(CO)₂ dicarbonyl species. In contrast, the oxidation state of V in VSiBEA changes strongly in function of calcinations in oxygen, outgassing at high temperature (773 K) and reducing with hydrogen at high temperature (873 K). This shows that lattice tetrahedral V species change easily oxidation state and this property allows them to be good candidate as active site of selective redox reactions.     

Towards the conception of an amperometric sensor of l-tyrosine based on Hemin/PAMAM/MWCNT modified glassy carbon electrode

A novel amperometric sensor was fabricated based on the immobilization of hemin onto the poly (amidoamine)/multi-walled carbon nanotube (PAMAM/MWCNT) nanocomposite film modified glassy carbon electrode (GCE). Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and ultraviolet visible (UV-vis) adsorption spectroscopy were used to investigate the possible state and electrochemical activity of the immobilized hemin. In the Hemin/PAMAM/MWCNT nanocomposite film, MWCNT layer possessed excellent inherent conductivity to enhance the electron transfer rate, while the layer of PAMAM greatly enlarged the surface average concentration of hemin (Γ) on the modified electrode. Therefore, the nanocomposite film showed enhanced electrocatalytical activity towards the oxidation of l-tyrosine. The kinetic parameters of the modified electrode were investigated. In pH 7.0 phosphate buffer solution (PBS), the sensor exhibits a wide linear range from 0.1 μM to 28.8 μM l-tyrosine with a detection limit of 0.01 μM and a high sensitivity of 0.31 μA μM⁻¹ cm⁻². In addition, the response time of the l-tyrosine sensor is less than 5 s. The excellent performance of the sensor is largely attributed to the electro-generated high reactive oxoiron (IV) porphyrin (O = Fe^IV-P) which effectively catalyzed the oxidation of l-tyrosine. A mechanism was herein proposed for the catalytic oxidation of l-tyrosine by oxoiron (IV) porphyrin complexes.     

Corrolazines: new frontiers in high-valent metalloporphyrinoid stability and reactivity

The activation of dioxygen and its analogues, such as hydrogen peroxide, by metalloporphyrins leads to the generation of high-valent metal-oxo species. This process is critically important to heme-catalyzed reactions, such as for cytochrome P450, and synthetic porphyrin-catalyzed oxidations. We have synthesized a new ring-contracted porphyrinoid system called a corrolazine that is designed to stabilize high oxidation states, including high-valent metal-oxo species. The corrolazine ligand stabilizes manganese(V) terminal oxo and terminal imido complexes for isolation, both of which are only transiently observed with normal porphyrin macrocycles. Examination of both oxygen atom transfer and hydrogen atom abstraction reactions for the Mn(V)-oxo complex has led to a number of mechanistic insights regarding these transformations. The activation of H 2O 2 to give the Mn(V)-oxo complex exhibits some dramatic and unexpected axial ligand effects that call into question the normal role of axial ligands in O-O bond cleavage pathways.     

Behaviors of plutonium and neptunium in nitric acid solutions containing hydrazine and technetium ions

The valence behaviors of plutonium and neptunium in the interaction of Pu(IV) and Np(V) with hydrazine and tetravalent uranium in technetium(VII)-containing aqueous nitric acid are reported. At [HNO₃] = 1 mol/l and Pu(IV) and Tc(VII) concentrations of ～0.1 and 0.01–0.2 mol/l, respectively, Pu(IV) is reduced to Pu(III) and is then entirely reoxidized to Pu(IV). Neptunium(V) in 1–3 M HNO₃ undergoes reduction to Np(IV) and then turns back into Np(V). The resulting solution usually contains a mixture of Np(IV) and Np(V). The reduction of Pu(IV) to Pu(III) and the reduction of Np(V) to Np(IV) are accompanied by hydrazine decomposition and by the reduction of most of the Tc(VII) to its lower valence forms. The conversions of Pu(III) into Pu(IV) and of Np(IV) into Np(V) are accompanied by the oxidation of these forms of technetium to Tc(VII). The introduction of diethylenetriaminepentaacetic acid into the reaction system makes Pu(III) more stable against reoxidation into Pu(IV) by reducing the hydrazine decomposition rate, enhances the conversion of Np(V) into Np(IV), and hampers Np(IV) oxidation to Np(V).     

Recent advances in synthetic transformations mediated by cerium(IV) ammonium nitrate

Cerium(IV) ammonium nitrate (CAN) has recently emerged as a versatile reagent for oxidative electron transfer; the overwhelming number of reports serve as a testimony to the unparalleled utility of CAN in a variety of transformations of synthetic importance. Our recent work has uncovered novel carbon-carbon bond-forming reactions leading to the one-pot synthesis of dihydrofurans, tetrahydrofurans, and aminotetralins. In addition, we have developed a number of facile carbon-heteroatom bond-forming reactions by the CAN-mediated oxidative addition of soft anions to alkenes. A mechanistic rationale has been provided for the reactions explored. As might be expected of very powerful one-electron oxidants, the chemistry of cerium(IV) oxidation of organic molecules is dominated by radical and radical cation chemistry.     

Mediated electrosynthesis with cerium (IV) in methanesulphonic acid

Methanesulphonic acid has been found to solubilize the Ce(III)/Ce(IV) couple. This makes cerium mediated electrosynthesis practical for commercial production of several carbonyl compounds. Results are presented for the electrochemical generation of Ce(IV) in methanesulphonic acid and for naphthalene oxidation to 1,4-naphthoquinone using Ce(IV).     

In situ XAS investigation of the oxidation state and local structure of vanadium in discharged and charged V2O5 aerogel cathodes

We have examined the evolution of the oxidation state and atomic structure of vanadium(V) in discharged and charged nanophase vanadium pentoxide (V₂O₅) aerogel cathodes under in situ conditions using X-ray absorption spectroscopy (XAS). We show that the oxidation state of V in V₂O₅ aerogel cathode heated under vacuum (100 μTorr) at 220 °C for 20.5 h is similar to that of V in a commercially obtained sample of orthorhombic V₂O₅. In addition, lithium (Li) insertion during the first cycle of discharging leads to the reduction of V(V) to V(IV) and V(IV) to V(III) in a manner consistent with the stoichiometry of the sample (i.e. Li_xV₂O₅). Li extraction during charging leads to oxidation of V(III) to V(IV) and then V(IV) to V(V). Furthermore, the oxidation state of V in fully charged cathodes remains unchanged with cycling (upto at least the 16th cycle) from that of V in the control V₂O₅ aerogel cathode. However, the average oxidation state of V in discharged V₂O₅ cathodes increased with cycling. Moreover, the local structure of V in the discharged state has a higher degree of symmetry than that of the fully charged state. A significant change in the structure of the VV correlation of discharged cathodes is observed with cycling indicating the formation of electrochemically irreversible phases.     

Electrochemical and spectral studies on the catalytic oxidation of nitric oxide and nitrite by high-valent manganese porphyrins at an ITO electrode

Catalytic oxidation of nitric oxide and nitrite by water-soluble manganese(III) meso-tetrakis(N-methylpyridinium-4-yl) porphyrin (Mn(III)(4-TMPyP) was first studied at an indium-tin oxide (ITO) electrode in pH 7.4 phosphate buffer solutions. A stepwise oxidation of Mn(III)(4-TMPyP) through high-valent manganese porphyrin species has been observed by electrochemical and spectroelectrochemical (OTTLE) techniques. The formal potential of 0.63 V for the formation of OMn(IV)(4-TMPyP) has been estimated from OTTLE data. The product, oxoMn(IV) porphyrin, was relatively stable decaying slowly to Mn(III)(4-TMPyP) with a first-order rate constant of 3.7 × 10⁻³ s⁻¹. OMn(IV)(4-TMPyP) has been found to oxidize NO catalytically at potentials about 70 mV more negative than that previously reported for OFe(IV)(4-TMPyP) with good selectivity against nitrite. Nitrite was catalytically oxidized at potentials higher than 1.1 V presumably by OMn(V)(4-TMPyP). OMn(IV)(4-TMPyP) was observed as an intermediate species. Nitrate has been confirmed to be a final product of the electrolysis at 1.2 V, while at 0.8 V nitrite left unchanged, demonstrating that OMn(IV)(4-TMPyP) could not oxidize nitrite. A possible schemes of the catalytic oxidation of NO by OMn^IV(4-TMPyP) and NO₂⁻ by OMn(V)(4-TMPyP) have been proposed.     

Antioxidants and stabilizers,CXIII. Oxidation products of the antidegradant ethoxyquin

In connection with the study of the mechanism of antioxidant action of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (ethoxyquin, I ) and of its ecological responses in stabilized polymers we studied its oxidation with some selected agents and the properties of products thus obtained. The oxidation of I with silver oxide or lead dioxide proceeds by two main routes. One of them leads to 8-(6-ethoxy-2,2,4-trimethyl-1,2-dihydro-1-quinolinyl)-6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline ( IV ), which is further oxidized to the blue compound 8-(6-ethoxy-2,2,4-trimethyl-1,2-dihydro-1-quinolinyl)-2,2,4-trimethyl-6-quinolone ( IX ). In the second route position 6 is attacked and 2,2,4-trimethyl-6-quinolone ( VII ) is formed, which is stable under the conditions used, but is oxidized further with m-chloroperbenzoic acid, giving rise to 2,2,4-trimethyl-6-quinolone-N-oxide ( VIII ). The oxidation of ethoxyquin with potassium permanganate also gives rise to dimer IV and not to 1,1′-bis(6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline) ( III ) reported in the literature. Potassium nitrosodisulfonate oxidizes I with formation of 6-ethoxy-2,2,4-trimethyl-8-quinolone ( X ). The oxidation of ethoxyquin with m-chloroperbenzoic acid gives rise to 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline-N-oxide ( V ) and dimer IV . Nitroxide V was obtained in the crystalline state. In the presence of acids, and particularly on the surface of silica gel it decomposes to ethoxyquin and nitrone VIII . Nitroxide V is readily reduced to the starting ethoxyquin. The transitionally formed 6-ethoxy-1-hydroxy-2,2,4-trimethyl-1,2-dihydroquinoline ( XIV ) readily disproportionates to I and V .     

Phase transformations in mesostructured vanadium–phosphorus-oxides

Mesostructured lamellar, hexagonal and cubic vanadium–phosphorus-oxide (VPO) phases were prepared employing cationic, anionic and alkylamine surfactants under mild conditions and low pH. The obtained mesophases displayed desirable vanadium oxidation states (+3.8 to +4.3) and P/V molar ratios 1.0 for the partial oxidation of n-butane to maleic anhydride. As-synthesized mesostructured VPO underwent phase transformations to various mesostructured and dense VPO phases depending on the post-synthesis treatment. The phase transformations of mesostructured VPO during Soxhlet extraction and thermal treatment in N₂ have been observed for the first time. These transformations were explained by the changes in the surfactant packing parameter, g. Calcination in air produced more disordered mesostructures and dense VPO phases such as γ-VOPO₄ and (VO)₂P₂O₇.     

Coordination Dynamics of Iron is a Key Player in the Catalysis of Non-heme Enzymes

Mononuclear nonheme iron enzymes catalyze a large variety of oxidative transformations responsible for various biosynthesis and metabolism processes. Unlike their P450 counterparts, non-heme enzymes generally possess flexible and variable coordination architecture, which can endow rich reactivity for non-heme enzymes. This Concept highlights that the coordination dynamics of iron can be a key player in controlling the activity and selectivity of non-heme enzymes. In ergothioneine synthase EgtB, the coordination switch of the sulfoxide radical species enables the efficient and selective C−S coupling reaction. In iron(II)- and 2-oxoglutarate-dependent (Fe/2OG) oxygenases, the conformational flip of ferryl-oxo intermediate can be extensively involved in selective oxidation reactions. Especially, the five-coordinate ferryl-oxo species may allow the substrate coordination via O or N atom, which may facilitate the C−O or C−N coupling reactions via stabilizing the transition states and inhibiting the unwanted hydroxylation reactions.     

Role of the Ti(IV)-Superoxide Species in the Selective Oxidation of Alkanes with Hydrogen Peroxide in the Gas Phase on Titanium Silicalite-1: An In Situ EPR Investigation

Abstract  

The interaction of TS-1 with gaseous hydrogen peroxide at temperatures above 373 K has been investigated by in situ EPR measurements. Treatment of TS-1 with hydrogen peroxide in the gas phase leads to a strong EPR signal, assigned to the Ti(IV)-superoxide species. In contrast to investigations with liquid hydrogen peroxide, here only one Ti(IV)-superoxide species could be detected in the EPR spectrum. The time constant of the reaction of the Ti(IV)-superoxide species detected by in situ EPR measurements was much larger than that observed for the rate of consumption of propane or propene via gas chromatographic analysis. Thus, we conclude that the superoxide species may take part in the oxidation reaction (via side reactions or the formation of unselective products), but is probably not the main responsible species in the oxidation of propane or propene.     

Thermodynamic assessment of the group IV,V and VI oxides for the design of oxidation resistant multi-principal component materials

Multi-principal component materials (MPCMs) are currently being investigated for use in high and ultra-high temperature environments. The design of oxidation resistant multi-component materials requires as input the oxidation behavior of each of the components. FactSage free energy minimization software and databases were used to calculate the equilibrium oxide phases and free energies of formation for the oxides of the Group IV, V and VI refractory metals, and their carbides, nitrides and borides. The results are summarized in Ellingham diagrams. Periodic trends were noted; Group IV elements form the most stable oxides with the highest melting temperatures (T_m), Group V elements form oxides with low T_m, and Group VI elements form gaseous oxide species. Oxygen diffusion data from literature for some of these oxides were also reviewed and summarized. The results are utilized to identify strategies for optimizing oxidation resistance of MPCMs for service at temperatures above 1700°C.     

Surface Doping of Rutile by Vanadium

A rutile monocrystal was surface-doped with vanadium by sintering with vanadium(V) or vanadium(IV) oxides and investigated by cyclic voltammetry. It is found that vanadium diffuses into the surface layer of rutile forming a mixed oxide. Vanadium atoms in the crystal lattice of rutile are tetravalent, but the vanadium atoms in the first monolayer may be both oxidized to the pentavalent as well as reduced to the trivalent oxidation state. These redox transformations are accompanied by the exchange of oxygen and/or protons between the surface layer of the crystal and the environment as well as the exchange of charge carriers (electrons) with the conduction band edge of rutile.