14314-91-1Relevant articles and documents
Unifying the Solution Thermochemistry of Molecules, Radicals, and Ions
Griller, D.,Simoes, J. A. Martinho,Mulder, P.,Sim, B. A.,Wayner, D. D. M.
, p. 7872 - 7876 (1989)
A general cycle was developed that defines the thermodynamics for all of the homolytic and heterolytic cleavage reactions of a hydrocarbon, R-R', in solution.Only seven experimental parameters were needed in order to define the energetics for all 11 of the possible cleavage reactions of R-R'.These parameters were the oxidation and reduction potentials of R-R', R(.), and R'(.) and the homolytic, R-R', bond energy.The utility of this approach was demonstrated for the case where R was an arylmethyl group and R' was hydrogen.The oxidation and reduction potentials of thearylmethyl radicals were measured by modulation voltammetry in acetonitrile, and the homolytic C-H bond energies of the corresponding hydrocarbons were measured by photoacoustic calorimetry.The cycle was also extended to a case where R-R' was a radical rather than a closed-shell molecule.
Generation of Arenium Ions by a Self-Protonation Reaction in an Aprotic Molten Salt Medium
Buchanan, A. C.,Dworkin, A. S.,Smith, G. P.
, p. 5262 - 5265 (1980)
We have examined the reaction behavior of a group of polycyclic aromatic hydrocarbons in the aprotic liquid SbCl3-10 mol percent AlCl3 from 100 to 130 deg C by 1H NMR and by quench and separation techniques.For anthracene, pyrene, 9,10-dimethylanthracene, 9,10-diphenylanthracene, and naphthacene, we have observed a novel arene self-protonation reaction for which the proton source is the condensation-dehydrogenation of a portion of the arene combined with arene oxidation by SbCl3.Naphthalene and phenanthrene, however, do not undergo this reaction.Evidence is presented which indicates that the self-protonation reaction proceeds through the oxidation of the arene to its radical cation by SbCl3, and that the function of AlCl3 is to enhance the oxidizing power of the Sb3+/Sb0 couple.
OPTICAL STUDIES OF HYDRONAPHTHYL RADICALS EMBEDDED IN DIHYDRONAPHTHALENE CRYSTAL.
Nakayama,Sheng
, p. 199 - 206 (1981)
Radiation-induced radicals in dihydronaphthalene were investigated at 4. 2 K by absorption, fluorescence and fluorescence excitation studies. It was shown that the radicals in dihydronaphthalene are hydronaphtyl radicals. The advantges of using the dihydro compounds in the identification of cyclohexadienyl type radicals is discussed.
Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation
Warren, Jeffrey J.,Mayer, James M.
scheme or table, p. 5282 - 5287 (2010/09/10)
Chemical reactions that involve net hydrogen atom transfer (HAT) are ubiquitous in chemistry and biology, from the action of antioxidants to industrial and metalloenzyme catalysis. This report develops and validates a procedure to predict rate constants for HAT reactions of oxyl radicals (RO ?) in various media. Our procedure uses the Marcus cross relation (CR) and includes adjustments for solvent hydrogen-bonding effects on both the kinetics and thermodynamics of the reactions. Kinetic solvent effects (KSEs) are included by using Ingold's model, and thermodynamic solvent effects are accounted for by using an empirical model developed by Abraham. These adjustments areshown to be critical to the success of our combined model, referred to as the CR/KSE model. As an initial test of the CR/KSE model we measured self-exchange and cross rate constants in different solvents for reactions of the 2,4,6-tri-tert-butylphenoxyl radical and the hydroxylamine 2,2′-6,6′-tetramethylpiperidin-1-ol. Excellent agreement is observed between the calculated and directly determined cross rate constants. We then extend the model to over 30 known HAT reactions of oxyl radicals with OH or CH bonds, including biologically relevant reactions of ascorbate, peroxyl radicals, and α-tocopherol. The CR/KSE model shows remarkable predictive power, predicting rate constants to within a factor of 5 for almost all of the surveyed HAT reactions.
Direct Comparison of the reactivity of model complexes for compounds 0, I, and II in oxygenation, hydrogen-abstraction, and hydride-transfer processes
Fertinger, Christoph,Hessenaue-Ilicheva, Natalya,Franke, Alicja,Van Eldik, Rudi
supporting information; scheme or table, p. 13435 - 13440 (2010/06/11)
The iron(III) meso-tetramesitylporphyrin complex is a good biomimetic to study the catalytic reactions of cytochrome P450. All of the three most discussed reactive intermediates concerning P450 catalysis (namely, Cpd 0, Cpd I, and Cpd II) can be selective
