Mechanistic Study on the Oxidation of Promazine and Chlorpromazine by Hexaimidazolcobalt(III) in Acidic Aqueous Media

The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a large excess of cobalt(III) and H⁺ ions using u.v.–vis. spectroscopy ([Co^III] = (1–6) × 10⁻³ m, [ptz] = (2.5–10) × 10⁻⁵ m, [H⁺] = 0.05–0.8 m, I = 1.0 m (H⁺, Na⁺, Cl⁻), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k_obs) on [Co^III] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined. Mechanistic consequences of all the results are discussed.     

六齿八羟基喹啉锰类配合物催化二甲亚砜的氧化消除

在NH4OAc和HOAc的促进下,使用环境友好的丙酮-水混合溶剂,六齿八羟基喹啉锰类配合物(Q3MnⅢ)能够高效地催化H2O2氧化二甲亚砜(DMSO).卤素取代的Q3MnⅢ配合物具有更高的催化活性,这归因于卤索取代基能加强Q3MnⅢ的畸变效应,这一点经B3LYP/6.311G+(d)计算得到证实.另外考察了一些因素对反应的影响,并提出了一个催化反应机理.     

Mechanistic Studies on the Oxidation of Hydroquinone by an Oxo-bridged Diiron(III,III) Complex in Weakly Acidic Aqueous Media

The kinetics of oxidation of hydroquinone (H₂Q) by a μ-oxo-bridged diiron(III,III) complex, Fe₂(μ-O)(phen)₄(H₂O)₂]⁴⁺ (1) has been investigated in aqueous media at 25.0 °C in presence of an excess of 1,10-phenanthroline (phen). The overall redox rate increases with increase in [H⁺]. The title complex (1) and its conjugate bases, [Fe₂(μ-O)(phen)₄(OH)₂]³⁺(2) and [Fe₂(μ-O)(phen)₄(OH)₂]²⁺ (3), participate in the reaction with H₂Q as the only kinetically reactive reducing species. Rate constants (in dm³ mol⁻¹ s⁻¹) for the parallel reactions (1) + H₂Q → Products, (2) + H₂Q → Products and that for (3) + H₂Q → Products are, respectively, 500 ± 40, 100 ± 6 and 30 ± 2. Substantial rate retardation in D₂O media in comparison to that in H₂O media suggests that electron transfer is coupled with proton movements in the rate-determining step.     

Mechanistic Studies on the Oxidation of Hydrazine by Tris(biguanide)manganese(IV) in Aqueous Acidic Media

The title Mn^IV complex, [Mn(LH₂)₃]⁴⁺ (LH₂ = biguanide = H₂NC(NH)NHC(NH)NH₂), an authentic two‐electron oxidant, quantitatively oxidizes hydrazine (H₂NNH₂) to dinitrogen in the pH interval 2.00–3.50. The net four‐electron oxidation of hydrazine is provided by two Mn^IV as established by stoichiometric studies. The overall reaction is composed of two parallel paths:     

Mechanistic Studies on the Oxidation of Nitrite by a μ‐Oxodiiron(III,III) Complex in Aqueous Acidic Media

Examined in this study is the kinetics of a net 2e⁻ transfer between [Fe₂(μ‐O)(phen)₄(H₂O)₂]⁴⁺ ( 1 ) and its hydrolytic derivatives [Fe₂(μ‐O)(phen)₄(H₂O)(OH)]³⁺ ( 2 ) and [Fe₂(μ‐O)(phen)₄(OH)₂]²⁺ ( 3 ) with in aqueous media and in presence of excess 1,10‐phenanthroline (phen). The reaction is quantitative with a 1 : 1 stoichiometry between the oxidant and reductant to produce ferroin ([Fe(phen)₃]²⁺) and . The order of reactivity of the oxidant species is 1 > 2 > 3 , in agreement with the progressive cationic charge reduction. The reactions appear to be inner‐sphere where the initial one‐electron proton‐coupled redox (1e⁻, 1H⁺; electroprotic) seems to be rate‐determining.     

Binuclear Homoleptic Manganese(III,III) and Manganese(IV,III) Complexes with Deprotonated D-Mannose from Aqueous Solution

Just a “reducing” sugar —namely, D -mannose—is a starting material in the synthesis of a mixed-valence complex of manganese in the oxidation states +III and +IV . Ba₂[Mn^IIIMn^IV(β-D -ManfH₋₅)₂]Cl⋅14 H₂O (Manf=mannofuranose; the structure of the anion is shown on the right) is prepared in aqueous solution by oxidation of an analogous Mn₂^III complex with oxygen. In neutral solutions the Mn^IIIMn^IV binuclear complex is formed by disproportionation of the Mn₂^III precursor.     

Detection of Oxidative Damage of Synthetic Oligonucleotides Caused by Thallium(III) Complexes

Biologically important short sequences of DNA were treated with Tl(III) complexes. The chloride complex releases the Tl(III) cation and therefore oxidizes DNA components and at concentrations higher than 50 nM cuts the strands. The cuts are well seen in the EQCM plots. The change in the strand structure is well seen at CD and UV‐Vis spectra. The chelate complexes of Tl(III) do not damage the DNA strands. The SERS spectra were particularly useful in demonstration of the chemical changes and orientation vs. the surface changes of particular groups in the strands after interaction with TlCl₄^?.     

Oxidative Degradation of l‐Isoleucine by Au3+ Complexes in Weakly Acid Medium: A Kinetic and Mechanistic Investigation

Oxidative degradation of l ‐isoleucine (Ileu) by Au³⁺ complexes has been studied spectrophotometrically in weakly acid medium (acetic acid–sodium acetate buffer, pH range 3.72–4.80) in the temperature range 288–308 K. The reaction is first order with respect to Au^III but complex order (<1) with respect to isoleucine. Ionic strength has no significant effect on the reaction kinetics. Both H⁺ and Cl⁻ ions have been found to show inhibiting effect on the reaction rate. Decreasing solvent polarity exerts an adverse effect on the reaction. Au³⁺ complexes react with the zwitterion form of isoleucine in a one‐step two‐electron transfer redox process. The reaction passes through intermediate formation of iminic cation, which hydrolyzes to produce 2‐methyl butanal, identified by ¹H NMR. The activation parameters ΔH ^≠ and ΔS ^≠ related to the rate‐limiting step of the reaction are evaluated. The derived rate law is in excellent agreement with the experimental results. The kinetic and activation parameters of this investigation have been compared and analyzed with those of the oxidation of l ‐leucine by gold(III).     

碳酸氢钠溶液中微量 Mn2+离子催化氧化降解有机污染物

 考察了微量 Mn2+离子在 NaHCO3 溶液中催化 H2O2 氧化降解有机污染物的性能. 结果表明, NaHCO3, MnCl2 和 H2O2 浓度分别为 25, 0.1 和 100 mmol/L 时, 在 25 oC 下反应 180 min 后亚甲基蓝可完全脱色, 化学耗氧量和总有机碳去除率分别达到 44.0% 和 13.8%. 该催化体系对甲基橙、罗丹明 B 以及垃圾渗滤液等都有较好去除效果. 紫外-可见光谱分析及反应动力学测试表明, MnIV=O 是该催化体系主要活性物种.     

Speciation of Aluminum(III) Complexes with Oxidized Glutathione in Acidic Aqueous Solutions

The structural speciation aspects, including the binding sites, species, complexation abilities and effects of the oxidized glutathione (GSSG) with aluminum(III) in aqueous solutions, have been studied by means of many analytical techniques: pH-potentiometry (25 degrees C, 0.1 M KCl and 37 degrees C, 0.15 M NaCl medium) was used to characterize the stoichiometry and stability of the species formed in the interactions of the Al(III) ion and the peptide GSSG, while multinuclear ((1)H, (13)C, (27)Al) nuclear magnetic resonance (NMR) and electrospray mass spectroscopy (ESI-MS) were applied to characterize the binding sites and species of the metal ion in the complexes. Two-dimensional ((1)H, (1)H-NOESY) was also employed to reveal the difference in the conformational behavior of the peptide and its complexes. The following results were obtained: (1) Aluminum(III) can coordinate with the important biomolecule GSSG through the following binding sites: glycyl and glutamyl carboxyl groups to form various mononuclear 1:1 (AlLH(4), AlLH(3), AlLH(2), AlLH, AlL, AlLH(-1), AlLH(-2)) and several binuclear 2:1 (Al(2)LH(4), Al(2)LH(2), Al(2)L) species (where H(6)L(2+) denotes the totally protonated oxidized glutathione) in acidic aqueous solutions. (2) It indicates that the COO(-) groups at low level of preorganization in such small peptide are not sufficient to keep the Al(III) ion in solution and to prevent the precipitation of Al(OH)(3) in the physiological pH range. (3) It also suggests that the occurrence of an Al-linked complexation, the conformation of the peptide GSSG in aqueous solutions appeared to change a little, relative to the initial structure.     

PNPP Hydrolysis Catalyzed by Manganese(III) Complexes with Crowned Salicylaldimine Schiff Base Ligand

Four manganese(III) complexes (MnL¹Cl, MnL²Cl, MnL⁴₂Cl, MnL⁵₂Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL³Cl and MnL⁶₂Cl, the crowned Schiff base manganese(III) complexes, MnL¹Cl, MnL²Cl, MnL⁴₂Cl and MnL⁵₂Cl, exhibit more high catalytic activity, which follow the order: MnL¹Cl >MnL²Cl >MnL⁴₂Cl >MnL⁵₂Cl >MnL³Cl >MnL⁶₂Cl; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL³Cl, 1.49 × 10³ times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10⁻⁴ mol dm⁻³.     

Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes

Reactions of nonheme Fe^III–superoxo and Mn^IV–peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)Fe^III(O₂)]^2? and [(TAML)Mn^IV(O₂)]^2?, with nitric oxide (NO) afford the Fe^III–NO₃ complex [(TAML)Fe^III(NO₃)]^2? and the Mn^V–oxo complex [(TAML)Mn^V(O)]^? plus NO₂^?, respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that M^III–peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)Fe^III(O₂)]^2? and [(TAML)Mn^IV(O₂)]^2? with NO, are converted into M^IV(O) and ^.NO₂ species through O?O bond homolysis of the peroxynitrite ligand. Then, a rebound of Fe^IV(O) with ^.NO₂ affords [(TAML)Fe^III(NO₃)]^2?, whereas electron transfer from Mn^IV(O) to ^.NO₂ yields [(TAML)Mn^V(O)]^? plus NO₂^?.     

State and Stability of Erbium(III) and Dysprosium(III) Complexes of Octaphenyltetraazaporphine in Proton-Donor Media

The acid-base interaction of chloro(octaphenyltetraazaporphinato)erbium(III), (acetylacetonato)(octaphenyltetraazaporphinato)erbium(III), and (acetylacetonato)(octaphenyltetraazaporphinato)dysprosium(III) in AcOH and in AcOH-benzene and AcOH-H₂SO₄ systems involves one meso-nitrogen atom of the complexes; the stability constants of the resulting acid forms were estimated. The solvoprotolytic dissociation of the complexes in the AcOH-H₂SO₄ system was studied, its kinetic parameters were determined, and some suggestions as to the dissociation mechanism were made.     

Versatile Catalytic Applications of Manganese(II,III) Schiff Base Complexes (Review)

Russian Journal of General Chemistry - Manganese forms a big number of complexes with Schiff bases that are extensively used as catalysts of oxidation, epoxidation, decarboxylation, coupling...     

Rhodium(III) and Iridium(III) Complexes with Octaphenyltetraazaporphine: Synthesis and Study of Their Acid Forms in Proton-Donor Media

The Rh(III) and Ir(III) complexes with octaphenyltetraazaporphine (X)MOPTAP (M = Rh, X = HSO₄, OH; M = Ir, X = HSO₄) are synthesized and their specific acid–base interactions in the CF₃COOH–CH₂Cl₂ and H₂SO₄–CH₃COOH systems are studied. The quantitative characteristics of equilibria between the acid and basic forms are obtained. The stability constants K ₁ of the first acid forms, in which one of the meso-N atom is protonated, for hydrosulfate (HSO₄)MOPTAP complexes in the H₂SO₄–CH₃COOH mixture are equal to –0.54 (Rh) and 0.0057 (Ir). The Ir complexes have more basic meso-N atoms due to more strong -backbonding effect of coordination and, therefore, the second protonation stage (K ₂ = –4.25) could be also observed. In the CF₃COOH–CH₂Cl₂ mixture, the basic properties of the meso-N atoms are levelled out. For (HSO₄)RhOPTAP K ₁ = 1.35, while for (HSO₄)IrOPTAP K ₁ = 1.24 and K ₂ = 0.45.     

Osmium(VIII)-Catalyzed Oxidation of Some Cyclic Amines by Potassium Hexacyanoferrate(III) in Alkaline Media: a Kinetics and Mechanistic Study

Reactions of morpholine, piperidine, and piperazine with Os(VIII)-catalyzed hexacyanoferrate(III) in alkaline media to produce the corresponding lactam have been studied at constant temperature and ionic strength. The reactions followed first-order kinetics with respect to [amine] and [Os(VIII)] but were independent of [Fe(CN)₆ ^3-] and [OH^-]. The effects of introduced electrolytes, potassium hexacyanoferrate(II), relative permitivity, and temperature have also been studied. A mechanism accounting for these results has been proposed.     

Studies of Cobalt(III) and Chromium(III) Complexes as Mediators in the Silver Nanoparticle Electrosynthesis in Aqueous Media

Metal complexes [Cr(bipy)₃]³⁺, [Co(bipy)₃]³⁺, and [Co(sep)]³⁺ in aqueous media at the potentials of M(III)/M(II) redox couple are shown playing a role of mediators in the electrosynthesis of silver nanoparticles, stabilized in a polyvinylpyrrolidone shell, by means of Ag(I) reduction. [Cr(bipy)₃]³⁺ is consumed under the conditions of long-term preparative electrolysis, the reduction process is accompanied by cathode passivation, therefore, the Ag+ ions complete conversion to the Ag-nanoparticles is unattainable. The two other metal complexes are fully remained unimpaired; the mediated electrosynthesis of the Ag-nanoparticles is carried out well effectively: the Ag-nanoparticles are produced in the solution bulk with a nearly quantitative yield, a theoretical charge being consumed. the [Co(bipy)₃]³⁺-mediated reduction of the Ag⁺ ions, generated by a silver anode in situ dissolution in the course of single compartment cell electrolysis, is accompanied by the anode metal dispersion and results in the formation of polydisperse Ag-nanoparticles. The summary Ag-nanoparticle current efficiency in the solution bulk comes to 128%. Thus formed Ag-nanoparticles are characterized by using dynamic light scattering, scanning and transmission electron microscopy, and X-ray powder diffraction. The Ag-nanoparticles are spherical, with a mean size of 83 ± 53 nm, or have a form of nanowires, with a length of l = 1216 ± 664 nm and diameter of d = 94 ± 17 nm. The [Co(sep)]³⁺-mediated AgCl reduction gives ellipsoidal Ag-nanoparticles sized l = 46 ± 19 nm, d = 27 ± 7 nm; the silver crystallite mean size is 20(1)–34.4(9) nm.     

Oxidation of Acyclovir by a Cuprate(III) Periodate Complex in Aqueous Alkaline Media: A Kinetic and Mechanistic Approach

The oxidation of acyclovir by diperiodatocuprate(III) in aqueous alkaline media, at a constant ionic strength of 0.01 mol?dm^?3, was studied spectrophotometrically at 25?°C. The reaction between acyclovir and DPC in alkaline media exhibits 1:4 stoichiometry (acyclovir:diperiodatocuprate(III)). The main oxidation products were identified by a spot test, along with infrared and liquid chromatography mass spectral studies. The oxidation reaction is first order with regard to the diperiodatocuprate(III) concentration, but has less than unit order in the acyclovir concentration and negative fractional orders in the periodate and alkali concentrations. Intervention of free radicals was observed in the reaction. The oxidation reaction in alkaline media was shown to proceed via a diperiodatocuprate(III)?Cacyclovir complex, which decomposes slowly in a rate determining step followed by subsequent fast steps to give the products. A suitable mechanism is proposed for these observations. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to the slow step of the mechanism, along with the thermodynamic quantities, were determined and discussed.     

[C^N]-Alkenyl Gold(III) Complexes by Proximal Ring-Opening of (2-Pyridyl)alkylidenecyclopropanes: Mechanistic Insights

Pyridine-substituted alkylidenecyclopropanes (Py-ACPs) react with gold(III) salts under mild reaction conditions through an unprecedented, proximal ring-opening pathway, to generate highly appealing, catalytically active pyridine alkenyl [C^N]-gold(III) species. Mechanistic studies reveal that the activation of the C−C bond of the ACP takes place through an unusual concerted, σ-bond metathesis type-process.