Reactive species hydroperoxide anion

The mechanism of the reaction is believed to be that shown in equation (9), this bong a specific example of equation (1), with hydroperoxide anion being the reactive species. Detailed study has led to the proposal of various transition states at different pH values.However, the reaction may be carried out satisfactorily over a wide range of concentrations of base and hydrogen peroxide providing that the reaction mixture is kept alkaline, as otherwise radical reactions may intervene with deleterious stereochemical consequences. 

The activity of the carbon supports needs to be evaluated for each catalyst material to be tested. An important finding was that metal-free Vulcan XC-72R (i.e., carbon black only) cathodes produced significant currents (Ppeak = 22mWcm and Vqc = 0.88 V with Solvay ADP at 50°C). Carbons reduce O2 primarily through a 2e mechanism at high pH producing hydroperoxide anions (HO2 ), which may form highly reactive hydroxyl radical species. 

A study using a model reaction system consisting of cumene hydroperoxide (CHP), A,A-dimethyl-/)-toluidine (DMPT), and o-benzoic sulfimide (saccharin) in toluene (without reactive acrylic monomer) showed conclusively that the DMPT was depleted significantly during the initiation step of an anaerobic reaction. The saccharin concentration was unchanged during this process. The initiating species may be radical anions derived from DMPT rather than reactive free radicals derived from the CHP [17]. 

Molecular modeling of the Et NBr activated hydroperoxides decomposition. On the base of experimental facts mentioned above we eon-sider the salt anion and eation as well as acetonitrile (solvent) moleeule participation when model the possible stmcture of the reactive hydroperoxide - catalyst complex. Model of the substrate separated ion pair (Sub-SIP) is one of the possible realization of join action of the salt anion and eation in hydroperoxide moleeule activation. In this complex hydroperoxide molecule is located between cation and anion species. For the sym-metrie molecules such as benzoyl peroxide [16], lauroyl peroxide [17], and dihydroxydicyclohexyl peroxide [18] attack of salts ions is proposed to be along direction of the peroxide dipole moment and perpendicularly to the peroxide bond. Hydroperoxides are asymmetric systems, that is why different directions of ion s attack are possible. The solvent effect can be considered by means of direct inclusion of the solvent molecule to the complex stmcture. From the other hand methods of modem computer... 

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