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.     

Oxoiron(V) Complexes of Relevance in Oxidation Catalysis of Organic Substrates

The selective oxidation of alkane and olefin moieties are reactions of fundamental importance in both chemical synthesis and biology. Nature efficiently catalyzes the oxidation of hydrocarbons using iron-dependent enzymes, which operate through the mediation of oxoiron(IV) or oxoiron(V) species. In the quest for chemo, regio and stereoselective transformations akin to those taking place in nature, bioinspired iron catalysts have been developed and understanding their mechanism of action has become a particularly relevant area of research. While a prominent advance in the preparation and characterization of oxoiron(IV) species has been accomplished, oxoiron(V) species remain exceedingly rare, presumably because the high reactivity that makes them particularly interesting also makes them difficult to observe. This review summarizes the advances in the field, focusing in synthetic systems for which the oxoiron(V) species relevant in these transformations have been directly detected and spetroscopically characterized.     

Visible-light photolysis of corrole-manganese(IV) nitrites to generate corrole-manganese(V)-oxo complexes

Photolysis of highly photo-labile corrole-manganese(IV) nitrites by visible light was studied in three corrole systems with different electronic environments. As observed in all three systems, homolytic cleavage of ON bond of nitrite ligand resulted in one-electron photo-oxidation to generate manganese(V)-oxo corroles, as determined by their distinct UV–vis spectra and kinetic behaviors. The spectral and kinetic results are rationalized by a multiple oxidation model, where the electron-demand Mn^V-oxo species may serve as direct two-electron oxidant for oxygen atom transfer reactions and less electron-demand systems undergo a disproportionation reaction to form a putative manganese(VI)-oxo corrole as the true oxidant.     

A STUDY OF COMPLEXES YIELDED BY HNO3 Fe(III)AND Eu(III) EXTRACTION FROM NITRATE MEDIA WITH ACIDIC Zr(IV) AND Hf( IV) DI-2-ETHILHEXYLPHOSPHATES

Possible reasons for significant enhancement of solvent extraction of some metals with dialkylphos-phoric acids in the presence of Zr(IV) and Hf(IV) are critically discussed, taking into consideration both the literature and the autors'data on the structure of acidic salts formed by these acids with Zr(IV) and Hf(IV). The chemistry of extraction of nitric acid, FeUII) and Eu ( I I I ) with Zr(IV) and Hf(IV) salts of di-2-ethy1hexy1 phosphoric acid (HX) has been studied using IR and ³¹P NMR spectroscopy. Nitric acid is extracted by these salts due to interaction with their acceptor sites that results in the formation of a new polymeric extractant with bidentate anions of two types, (X-H-X)- and (X-H-N0₃)_. Protons of these groups can be exchanged with metal cations extracted, e.g., with Fe(III) or Eu(I 11 ), heteropolynuc1 ear complexes with non-equivalent (chelating and bridge) N0₃ anions being formed during the extraction. The composition and structure of coordination polyhedrons formed around Zr(IV), Hf(IV), Fe(III) and Eu(III) have been determined. The reasons for a higher extraction ability of the salts studied for Fe(III) and Eu(III) versus D2EHPA itself are described.     

The Redox Chemistry of Manganese(III) and -(IV) Complexes

The oxidation-reduction thermodynamics for the manganese(III), -(IV), and -(II) ions, and their various complexes, are reviewed for both aqueous and aprotic media. In aqueous solutions the reduction potential for the manganese(III)/(II) couple has values that range from +1.51 V vs. NHE (hydrate at pH 0) to −0.95 V (glucarate complex at pH 13.5). The Mn(IV)/(III) couple has values that range from +1.0 V (solid Mn^IVO₃ at pH 0) to −0.04 V (tris gluconate complex at pH 13.5). With anhydrous media the propensity for the Mn(III) ion to disproportionate to solid Mn^IVO₂ and Mn(II) ion is avoided. For aprotic systems the range of redox potentials for various manganese complexes is from +2.01 V and +1.30 for the Mn(IV)/(III) and Mn(III)/(II) couples (bis terpyridyl tri-N-oxide complex in MeCN), respectively, to −0.96 V for the Mn(IV)/(III) couple (tris 3,5,-di-tert-butylcatecholate complex in Me₂SO). The redox reactions between manganese complexes and dioxygen species (O₂, O₂, and H₂O₂) also are reviewed.     

Methods for correction of selectivity of N-(2-sulfoethyl)chitosan-based materials towards platinum(IV) and palladium(II) ions

In this paper, we report methods for correction of selectivity of sorbents based on N-(2-sulfoethyl)chitosan towards platinum(IV) and palladium(II) in HCl solutions. The common method for correction of selectivity of the sorbents is variation of their modification degree with complexing groups. An increase in the degree of sulfoethylation of the chitosan leads to the significant increase in selectivity of sorption of palladium(II) over platinum(IV). Application of the N-(2-sulfoethyl)chitosan with the highest degree of sulfoethylation allows for selective separation palladium(II) from platinum(IV) (рН = 5.0). Palladium is quantitatively desorbed from the surface of the N-(2-sulfoethyl)chitosans by 3.5 mol/dm³ solution of HCl.     

Elution Behavior of Metal Ions with Mixed Glycine-Nitric Acid Eluents in Dowex 50W-X8 Column: Separation of Th(IV), Ce(IV), Bi(III), Fe(III), and Al(III)

Abstract

Distribution coefficients (K) determined by the batch technique in acidic glycine media using Dowex 50W-X8 cation exchanger (H⁺?form, 100–200 mesh size) revealed that this medium can effectively be employed to separate a number of tetravalent and trivalent metal ions from bivalent metal ions. In fixed glycine (0.40 M) and varying concentration of nitric acid (0.10 to 1.0 M), a number of mixtures containing two or three metal ions were resolved on columns using about 8 g of exchanger. In 0.40 M glycine-1.0 M HNO₃ medium, Th(IV)/Ce(IV) were separated from Al(III)/Fe(III)/Bi(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I) and also Al(III)/Bi(III) from a number of divalent metal ions. In 0.40 M glycine-0.50 M HNO₃ medium, the resolution of following ternary mixtures were also achieved: Th(IV)/Ce(IV)-Al(III)/Bi(III)-Fe(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I). Th(IV)/Al(III)/Fe(III)/Bi(III) were also separated from other divalent metal ions in 1.60 M glycine-0.50 M HNO₃ medium. The values of K, elution characteristics of metal ions, elution curves, and the results of the resolution of a number of mixtures of metal ions along with standard deviations are reported.     

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.     

EXTRACTION OF PALLADIUM(II) AND PLATINUM(IV) AS CHLOROCOMPLEX ACIDS INTO BASIC ORGANIC SOLVENTS

Solvent extraction of platinum(IV) and palladium(II) with tri-n-octylamine(TOA) in o-xylene from 4.0M (Na,H)(Cl, HSO₄) has been investigated at 298K in order to compare with similar extraction by trioctylphosphine oxide(TOPO). The dependence of the distribution ratio of platinum(IV) and pal 1adium(II) on TOA, hydrogen ion and chloride ion concentrations suggests the dominant extracted species of these metals would be 2:1 for proto-nated amine : chlorocomplex anion and the extraction should be essentially anion exchange reaction. The extraction constants (Kex = D[H⁺(T0A)C1 ] ²[C1 ]²), were evaluated as 10^6-3 and 10^5.8 for platinum(IV) and pal ladium(II), respectively. The anion exchange with protonated TOPO salt represented by H(T0P0)₂ ⁺C1  is less than that with protonated TOA salt by a factor of one order.     

Polybenzimidazole resin based new chelating agents. Palladium(II) and platinum(IV) sorption on resin with immobilized dithiooxamide

Microporous polybenzimidazole (PBI) of 250–500 μm bead size has been epoxidized and subsequently reacted with dithiooxamide in the presence of a phase-transfer catalyst to obtain a sorbent with immobilized dithiooxamide, EPBI(DTOX). The sorption of Pd(II) and Pt(IV) in HCl solutions has been measured on both PBI and EPBI(DTOX) resins, employing the sorbate species singly, in mixtures, and in the presence of a number of base metal ions, which include Cu(II), Ni(II), Zn(II), Co(II), Fe(II) and Fe(III). The saturation sorption capacities (mg/g dry resin) of PBI for Pd(II) and Pt(IV) in 0.1 N HCl are 276 and 288, respectively, the corresponding values for EPBI(DTOX) being 157 and 168. The sorption capacities decrease with the acid strength of the medium, the change, however, being relatively more pronounced for PBI, so much so that in concentrated (> 1 N) acids the sorption of EPBI(DTOX) is higher than that of PBI. In mixtures of Pd(II) and Pt(IV) with 10-fold molar excess of Pt(IV), PBI and EPBI(DTOX) show, respectively, 80% and 85% selectivity for Pd(II). While EPBI(DTOX) exhibits high selectivity (> 85% and > 80%, respectively) for Pd(II) and Pt(IV) in the presence of 100-fold molar concentration of any of the above base metal ions, on PBI, however, the Pd(II) and Pt(IV) selectivities are reduced to 50% and 20%, respectively, by 100-fold molar concentration of Fe(II).The neutral chelating ligand thiourea causes rapid stripping of Pd(II) and Pt(IV) from PBI and EPBI(DTOX) resins. The sorbed metal ions on PBI, being bound as complex anions by ionic forces, are more easily stripped by strong acids than the sorbed metal ions which are bound to EPBI(DTOX) by chelation. Having a relatively lower binding constant, Pt(IV) is however more easily stripped than Pd(II), thus permitting a selective stripping of Pt(IV) on PBI. On the other hand, a selective stripping of Pd(II) can be achieved with a strong solution of thiocyanate, which prevents stripping of Pt(IV) while allowing that of Pd(II). Thus, separation of Pd(II) and Pt(IV) in mildly acidic solutions in the absence of Fe(II) can be conveniently achieved by sorption on PBI followed by stripping with a strong solution of thiocyanate. EPBI(DTOX), on the other hand, is more useful for separation in concentrated acid solutions and in the presence of large concentrations of base metal ions including Fe(II).     

Selective Pd(II) and Pt(IV) sorption using novel polymers containing azamacrocycle functional groups

The synthesis of a new coordinating polymer containing nitrogen atoms by the copolymerization of a 15-membered triolefinic azamacrocycle, 9, named (E,E,E)-1-[(4-methylphenyl)sulfonyl]-6-[(2-trimethylsilylethyl)sulfonyl]-11-[(4-vinylphenyl)sulfonyl)]-1,6,11-triazacyclopentadeca-3,8,13-triene, with styrene is achieved. The novel polymeric material is characterized by means of elemental analysis, IR, ¹³C-CP MAS, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. We also report the study of palladium and platinum sorption from acidic solutions. A capacity of 0.36 mmol g⁻¹ of polymer for Pd(II) and 0.28 mmol g⁻¹ of polymer for Pt(IV) is determined by the batch-mode. The functionalised polymer presents a high selectivity towards precious metals over base metals such us Cu(II) and Ni(II).     

Components of male aggregation pheromone of strawberry blossom weevil, Anthonomus rubi herbst. (Coleoptera:Curculionidae)

The strawberry blossom weevil, Anthonomus rubi, is a major pest of strawberries in the United Kingdom and continental Europe. As part of a project to develop noninsecticidal control methods, the pheromone system of this species was investigated. Comparison of volatiles produced by field-collected, overwintering individuals of each sex led to identification of three male-specific compounds—(Z)-2-(3,3-dimethylcyclohexylidene)ethanol, (cis)-1-methyl-2-(1-methylethenyl)cyclobutaneethanol, and 2-(1-methylethenyl)5-methyl-4-hexen-1-ol (lavandulol)—in amounts of 6.1, 1.2, and 0.82 g/day/male. The first two compounds are components of the aggregation pheromone of the boll weevil, Anthonomus grandis, grandlure II and grandlure I, respectively. Grandlure I was the (1R,2S)-(+) enantiomer and lavandulol was a single enantiomer, although the absolute configuration was not determined. Trace amounts of the other two grandlure components (Z)-(3,3-dimethylcyclohexylidene)acetaldehyde (grandlure III) and (E)-(3,3-dimethylcyclohexylidene)acetaldehyde (grandlure IV) were also detected. (E,E)-1-(1-Methylethyl)-4-methylene8-methyl-2,7-cyclo-decadiene (germacrene-D), a known volatile from strawberry plants, Fragaria ananassa, was collected in increased amounts in the presence of pheromone-producing weevils. Male weevils only produced pheromone on F. ananassaand not on scented mayweed, Matracaria recutita, or cowparsley, Anthriscus sylvestris, although these are known food sources. In field trials using various combinations of synthetic grandlures I, II, III, and IV and lavandulol, significantly more weevils were caught in traps baited with blends containing grandlure I and II and lavandulol than in those baited with blends without lavandulol or unbaited controls. Addition of grandlure III and IV had no significant effect on attractiveness. Horizontal sticky traps were found to be more effective than vertical sticky traps or standard boll weevil traps. In mid-season females predominated in the catches, but later more males than females were trapped.     

Extraction and recovery of cerium(IV) along with fluorine(I) from bastnasite leaching liquor by DEHEHP in [C8mim]PF6

BACKGROUND: Ionic liquids (ILs) as environmentally benign solvents have been widely studied in the application of solvent extraction. However, few applications have been successfully industrialized because of the difficult stripping of metal ions or the loss of components of the ILs. More work needs to be done to investigate the extraction behaviour of IL‐based extraction systems. In this work, the extraction behaviour of Ce(IV), Th(IV) and some trivalent rare earth (RE) nitrates by di(2‐ethylhexyl) 2‐ethylhexylphosphonate (DEHEHP) in the IL, 1‐methyl‐3‐octylimidazolium hexafluorophosphate ([C₈mim]PF₆), was investigated and compared with that in the n‐heptane system. In particular, the effect of F(I) on the extraction mechanism for Ce(IV) and its separation from Th(IV) was investigated. Otherwise, the recovery efficiency of Ce(IV) and F(I) from a practical bastnasite leach liquor was examined using IL based extraction. RESULTS: Similar selectivity (Ce(IV) > Th(IV) ? RE(III)) was observed in both the IL and n‐heptane systems. The existence of F(I) had a large negative impact on the extraction and separation of Ce(IV). An identical process for the extraction of Ce(NO₃)₄ containing F(I) by DEHEHP in both IL and n‐heptane was achieved under appropriate conditions. The Ce(IV) in the IL phase may be quantitatively back extracted and may be recovered as part of high purity CeF₃ and cerium sulfate. CONCLUSION: It is possible for IL to act as an environmentally benign solvent for the recovery of Ce(IV) and F(I) from bastnasite in rare earth hydrometallurgy. Copyright © 2009 Society of Chemical Industry     

Carbonic Anhydrase Inhibitors. Part 46 Inhibition of Carbonic Anhydrase Isozymes I, II and IV With Trifluoromethylsulfonamide Derivatives and Their Zinc(II) and Copper(II) Complexes

Reaction of aromatic/heterocyclic sulfonamides containing a free amino group with triflic anhydride afforded compounds possessing trifluoromethanesulfonamido moieties in their molecule. The Zn(II) and Cu(II) complexes of these new sulfonamides were prepared and characterized by standard procedures (elemental analysis, spectroscopic, magnetic, thermogravimetric and conductimetric measurements). The new derivatives showed good inhibitory activity against three isozymes of carbonic anhydrase (CA), i.e., CA I, II and IV.     

Non-heme Fe(IV)-oxo intermediates

High-valent non-heme iron-oxo intermediates have been proposed for decades as the key intermediates in numerous biological oxidation reactions. In the past three years, the first direct characterization of such intermediates has been provided by studies of several alphaKG-dependent oxygenases that catalyze either hydroxylation or halogenation of their substrates. In each case, the Fe(IV)-oxo intermediate is implicated in cleavage of the aliphatic C-H bond to initiate hydroxylation or halogenation. The observation of non-heme Fe(IV)-oxo intermediates and Fe(II)-containing product(s) complexes with almost identical spectroscopic parameters in the reactions of two distantly related alphaKG-dependent hydroxylases suggests that members of this subfamily follow a conserved mechanism for substrate hydroxylation. In contrast, for the alphaKG-dependent non-heme iron halogenase, CytC3, two distinct Fe(IV) complexes form and decay together, suggesting that they are in rapid equilibrium. The existence of two distinct conformers of the Fe site may be the key factor accounting for the divergence of the halogenase reaction from the more usual hydroxylation pathway after C-H bond cleavage. Distinct transformations catalyzed by other mononuclear non-heme enzymes are likely also to involve initial C-H bond cleavage by Fe(IV)-oxo complexes, followed by diverging reactivities of the resulting Fe(III)-hydroxo/substrate radical intermediates.     

EXTRACTION OF TITANIUM(IV) FROM AQUEOUS HYDROCHLORIC ACID SOLUTIONS INTO ALAMINE 336-M-XYLENE MIXTURES

Extraction of Ti(IV) from its aqueous hydrochloric acid solutions into organic Alamine 336-m-xylene systems was investigated. Extraction experiments were conducted with three different initial metal concentrations of 1, 3, and 6 mg/mL, each at three acidic molarities of 1, 5, and 10 M. It was observed that the extractability of Ti(IV) increases with increasing acidic molarities. Alamine 336 diluted with m-xylene was found to be a suitable extractant for Ti(IV) across this acidic range. In parallel, a mathematical model was developed to correlate metal extractability and Alamine 336 volume content. Optimal Alamine 336 contents were estimated for single-stage extraction.     

Separation and Purification of Quinolone Alkaloids from the Chinese Herbal Medicine Evodia rutaecarpa (Juss.) Benth by High Performance Counter-Current Chromatography

Preparative separation of quinolone alkaloids in Evodia rutaecarpa (Juss.) Benth was conducted by high performance counter-current chromatography (HPCCC) with a pair of two solvent systems consisting of n-hexane-methanol-water-acetic acid (2:1:1:0.2, v/v) and (5:4:2:0.1, v/v). Consequently, 31.78 mg 1-methyl-2-nonyl-4 (1H)-quinolone (I), 59.25 mg 1-methyl-2-(6-undecenyl)-4 (1H)-quinolone (II), 333.27 mg evocarpine (III), 101.13 mg 1-methyl-2-(6,9-pentadecadienyl)-4(1H)-quinolone (IV), 132.17 mg dihydroevocarpine (V), and 86.99 mg 1-methyl-2-(10-pentadecenyl)-4(1H)-quinolone (VI) were obtained from 1.3 g of the crude extract. The structures of these compounds were identified by mass spectrometer (MS), nuclear magnetic resonance (¹H NMR and ¹³C NMR).     

EXTRACTION OF TITANIUM(IV) FROM AQUEOUS HYDROCHLORIC ACID SOLUTIONS INTO ALAMINE 336-M-XYLENE MIXTURES

Extraction of Ti(IV) from its aqueous hydrochloric acid solutions into organic Alamine 336-m-xylene systems was investigated. Extraction experiments were conducted with three different initial metal concentrations of 1, 3, and 6 mg/mL, each at three acidic molarities of 1, 5, and 10 M. It was observed that the extractability of Ti(IV) increases with increasing acidic molarities. Alamine 336 diluted with m-xylene was found to be a suitable extractant for Ti(IV) across this acidic range. In parallel, a mathematical model was developed to correlate metal extractability and Alamine 336 volume content. Optimal Alamine 336 contents were estimated for single-stage extraction.     

Synthesis,Composition, and Ion-Exchange Behavior of Thermally Stable Zr(IV) and Ti(IV) Arsenophosphates: Separation of Metal Ions

Abstract

Two new inorganic ion-exchange materials, Zr(IV) and Ti(IV) arsenophosphates, have been synthesized. They are reproducible in behavior and possess excellent thermal stability. Their tentative structures have been proposed based on pH titrations, thermogravimetry, chemical analysis, IR studies, and other ion-exchange properties. Distribution studies of some metal ions have also been made on the basis of which several useful binary separations have been achieved such as Fe(III) from VO(II), Cu(II), and Zn(II); Pb(II) from Cu(II), Hg(II), and Zn(II); Ti(IV) from UO₂(II) and Ce(IV); and Mg(II) from Sr(II) and Ba(II).