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Redox Catalysis (redox + catalysis)

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Chemistry	100%

Selected Abstracts

Electrocarboxylation of Benzyl Halides through Redox Catalysis on the Preparative Scale

CHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2006
Onofrio Scialdone Dr.
Abstract The electrocarboxylation of benzyl halides to the corresponding carboxylic acids through homogeneous charge-transfer catalysis was investigated both theoretically and experimentally to determine the influence of the operative parameters on the yield of the process and on the catalyst consumption. Theoretical considerations, based on fast kinetics of redox catalysis, were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane catalyzed by 1,3-benzenedicarboxylic acid dimethyl ester performed at a carbon cathode under different operative conditions. We obtained high yields of the target carboxylic acid and experienced a low catalyst consumption by operating with optimized [RX]bulk/[CO2]bulk and [RX]bulk/[catalyst] ratios. [source]

Electrostatic Assembly of a Redox Catalysis System for Detection of Glutamate

ELECTROANALYSIS, Issue 24 2006
Alice
Abstract Interfacial assemblies capable of determining glutamate by redox catalysis are prepared by electrostatic assembly of alternating layers of ferrocene poly(allylamine) polymer and glutamate oxidase on a gold electrode. Deposition of the polymer was confirmed in cyclic voltammetry measurements by the presence of a surface wave corresponding to the oxidation of the ferrocene group. In the presence of glutamate in the adjacent electrolyte solution, the current increases and approaches a pseudosteady state, consistent with redox catalysis. Electrodes modified with glutamate oxidase had a linear response to glutamate up to 0.0045,M with sensitivity of 20,,A/cm2 and a limit of detection of 31.4,,M glutamate. An apparent Michaelis,Menten constant of 0.40(±0.13),mM for the confined glutamate oxidase was determined for this assembly. When used in flow-injection experiments, glucose oxidase modified electrodes responded to transient zones of glucose; however, the detection limits of the assemblies to the flowing stream were substantially higher than found for measurements on static solutions. [source]

Radical clocks and electron transfer.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 12 2005
Comparison of crown ether effects on the reactivity of potassium, magnesium towards 1-bromo-2-(3-butenyl)benzene.
Abstract The reaction of the title precursor of the aryl radical clock 1-bromo-2-(3-butenyl)benzene, 1Br, towards potassium and magnesium in THF was studied in the presence and absence of various additives, at ambient and low temperatures. The additives were cis -dicyclohexano-18-crown-6 or tert -butyl alcohol; the first one to render soluble potassium by forming its alkalide, the second to distinguish carbanionic from radical cyclization. The addition of 1Br to a THF stirred suspension of potassium pieces yields remarkably low amounts of products resulting from radical cyclization, in contrast to the amounts reported by Bunnett and Beckwith's group for the reaction in 67% ammonia,33% tert -butyl alcohol medium. The amount of cyclized products obtained with potassium pieces in THF is in the same range as that observed in the reaction of magnesium with 1Br in THF. This similarity allows us to discard the earlier triad hypothesis that we proposed to account for the unexpectedly low amounts of cyclized products of aryl halides radical clocks in Grignard reagent formation. The addition of crown ethers to the THF reaction medium induces contrasting effects for potassium and magnesium. A distinctive increase in the radical cyclization is observed for potassium, whereas the addition of crown inhibits the formation of Grignard reagent more efficiently when the solvent is diethyl ether than when it is THF. The observed effects are explained by putting in perspective the metal reactive dissolution with elementary steps occurring in the vicinity of a cathode. The reaction of potassium pieces or magnesium turnings is comparable to the heterogeneous electron transfer occurring at a cathode whereas the reaction of potassium in the presence of crown ether is comparable to homogeneous conditions of electron transfer obtained in redox catalysis. A discussion of the dianion hypothesis for the Grignard reaction of aryl halides is provided and the importance of considering the reactivity of reactive metal dissolution (or organic corrosion) in the framework of recent progress made in the modelling of electrode reactivity is emphasized. This paper shows that caution should be taken when radical clocks are used to study reactions at the metal,solution interface. More specifically, the non-observation of rearranged products from the radical clock (even for the very rapid ones) under these conditions does not necessary imply that there is no radical intermediate along the dominant reaction channel. This pattern of reactivity strongly contrasts with that usually observed when radical clocks are used in homogeneous media. The leading parameters in the rearranged/unrearranged products ratio seem to be the time that the reactive species (radical anions) created by the first electron transfer spend in the close vicinity of this surface, the rate constant of rearrangement of the radical formed by the cleavage of the radical anion and the redox properties of this radical. Copyright © 2005 John Wiley & Sons, Ltd. [source]

Electron Transfer to Sulfides and Disulfides: Intrinsic Barriers and Relationship between Heterogeneous and Homogeneous Electron-Transfer Kinetics

CHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2007
Belèn Meneses
Abstract The electron-acceptor properties of series of related sulfides and disulfides were investigated in N,N -dimethylformamide with homogeneous (redox catalysis) and/or heterogeneous (cyclic voltammetry and convolution analysis) electrochemical techniques. The electron-transfer rate constants were determined as a function of the reaction free energy and the corresponding intrinsic barriers were determined. The dependence of relevant thermodynamic and kinetic parameters on substituents was assessed. The kinetic data were also analyzed in relation to corresponding data pertaining to reduction of diaryl disulfides. All investigated reductions take place by stepwise dissociative electron transfer (DET) which causes cleavage of the CalkylS or SS bond. A generalized picture of how the intrinsic electron-transfer barrier depends on molecular features, ring substituents, and the presence of spacers between the frangible bond and aromatic groups was established. The reduction mechanism was found to undergo a progressive (and now predictable) transition between common stepwise DET and DET proceeding through formation of loose radical anions. The intrinsic barriers were compared with available results for ET to several classes of dissociative- and nondissociative-type acceptors, and this led to verification that the heterogeneous and the homogeneous data correlate as predicted by the Hush theory. [source]