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Showing 1 to 13 of 13 for “"radical anions"”.
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Rearrangements of Radical Anions Generated from Cyclopropyl Ketones
… assumption in such studies is that if a "radical" species is produced, it will undergo ring opening. We have found that there are two important factors to consider in the design of SET probes: 1) ring strain, the thermodynamic driving force for the rearrangement, and 2) resonance energy, …
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The electrochemical behavior and electronic structure of non- transition metal chelate radical anions
… of reversible one-electron reduction to the radical ion. These ion radicals are extremely stable, having been kept for many months at room temperature under argon atmosphere. Previous studies have indicated that the dianion radical of the substituted acetylacetonate ligand itself is extremely …
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The Reaction Kinetics of Neutral Free Radicals and Radical Ions Studied by Laser Flash Photolysis
t-Butoxyl radical has been used as a chemical model for hydrogen abstractions in many enzymatic and biological systems. However, the question has arisen as to how well this reactive intermediate mimics these systems. In addressing this concern, absolute rate constants and Arrhenius parameters for …
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Mass spectrometric characterization of remotely charged amino acids and peptides
… structure of 3- and 4-pyridinylnitrene-n-oxide radical anions. Reactions with nitric oxide are generally similar to those reported previously for other aromatic nitrene radical anions. In particular, phenoxide formation by nitrogen–oxygen exchange is observed with both isomers. Oxygen atom …
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The Chemistry of Aroyl Azides in Piperidine- and Steroid-Separated Bichromophoric System: Photoinduced Long-Distance Intramolecular Electron Transfer Reactions
… intermediate states. The aryl amine radical cations were detected by pulsed laser spectroscopy and the highly reactive aroyl azide radical anions were identified by the results of steady-state photolysis. In acetonitrile and in methyl alcohol solution, the photoexcited aryl amine …
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The elucidation of single electron transfer (SET) mechanisms in the reactions of nucleophiles with carbonyl compounds
The chemistry of the radical anion generated from 1,I-dimethyl-5,7-di-tbutylspiro[ 2,5]octa-4,7-dien-6-one (<b>20</b>) was studied electrochemically using cyclic and linear sweep voltammetry (CV, LSV). The reduction potential of <b>20</b> was estimated to be -2.5 V VS. 0.1 M Ag⁺/Ag, similar to the …
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New Strategies and Transformations for the alpha-Functionalization of Amines to Access Chiral Amines
… of three synthons: 2-azaallyl anion, 2-azaaalyl radical and 2-azadiene. </p><p> We began investigating processes to access alpha-amino anions directly through alpha-deprotonation of imines (formation of 2-azaallyl anions). The alpha-amino anion was then utilized in two further reactions: 1. …
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Radical anion rearrangements. aryl cyclopropyl ketyl anions
… generated aryl cyclopropyl] ketyl anions, we have shown that the assumptions made in the use of these substrates as SET probes are not necessarily valid. Using derivative cyclic and linear sweep voltammetry it was discovered that the ketyl anions of alkyl- and unsubstituted aryl …
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Evaluation of 1,1-Dimethyl-5,7-Di-T-Butylspiro[2.5]Octa-4,7-Dien-6-One as a Mechanistic Probe for Single Electron Transfer
Single electron transfer (SET) mechanisms are becoming ubiquitous in modern organic chemistry. However, it is often difficult to distinguish SET mechanisms from polar mechanisms. Kinetics, products and product distributions, and response to perturbation in solvent and substituents are often …
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Studies of Molecular and Colloidal Semiconductors and Their Mass Transport Properties by Voltammetry, Stochastic Electrochemistry, and Electrogenerated Chemiluminescence
… was shown to be a function of generated radical cations and radical anions stability and their molecular structure. A high ECL efficiency (ΦECL > 0.6) of some of these compounds suggest their promising applications as light emitters in ECL devices.
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Synthesis of New Molecule-Based Magnets using Bridging Organic Radicals
Several new families of organic acceptors that are candidates as building blocks of molecule-based ferrimagnets were synthesized and characterized. These families include fluorodicyanostilbenes, a tetrachlorodicyanostilbene, naphthyltricyanoethylenes, bromophenyltricyanoethylenes, and an …
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Electrochemical synthesis of polyesters and polyamides. A study of the polymerisation of lactams, lactones and the anhydride/propylene oxide system by direct electrolysis of their conducting solutions
… was attempted by preparing living polystyryl anions electrochemically followed by the addition of E-caprolactone. The analysis by differential scanning calorimetry and gel permeation chromatography showed that the attempted block copolymer was composed of entirely mixtures of two homopolymers. …
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Coordination Geometries in Metallobundles Enforcing Oxidative and Hydrolytic Catalysis and Designing Biomaterials for Use As Antimicrobials
… grander O2-utilizing metalloproteins such as radical-generating ribonucleotide reductases and catalases. One notable family of de novo proteins is the Due Ferri or DF series of four-helix bundles providing a dinuclear site for metal incorporation and are amenable for tailoring active site …