Oxidative agents electrochemical oxidation

The transition states of the latter are therefore more sensitive to stereochemical and electronic influences, which also leads to a higher selectivity than in analogous electrochemical conversions. At some oxide electrodes, such as the Ni(OH)2 electrode [13], the oxidation occurs as inner sphere electron transfer by hydrogen atom transfer. Also at doped titanium anodes this seems to be partially the case [14]. It cannot be definitely excluded that also in some oxidations at platinum anodes, higher valency oxides at the surface act as inner sphere electron transfer agents. Electrochemical" inner sphere electron transfers are intentionally used in indirect electrochemical conversions where selective chemical oxidants or reductants are regenerated by electron transfer from the electrode [15]. They are also immobilized by attaching polymer-bound electrocatalysts as mediators to the electrode surface [16]. 

Pentafluorophenol is oxidized to different products depending on oxidation agents and reaction condibons The mtermediate is usually pentafluorophenoxy radical, which attacks the aromabc nng to give dimenc and tnmenc products Electrochemical oxidation of pentafluorophenol m hydrogen fluonde solvent and in the presence of a strong Lewis base or acid leads to a different rabo of products [61] (equation 55)... 

Reduction of fullerenes to fullerides — Reversible electrochemical reduction of Ceo in anhydrous dimethylformamide/toluene mixtures at low temperatures leads to the air-sensitive coloured anions Qo" , ( = 1-6). The successive mid-point reduction potentials, 1/2, at -60°C are -0.82, -1.26, -1.82, -2.33, —2.89 and —3.34 V, respectively. Liquid NH3 solutions can also be used. " Ceo is thus a very strong oxidizing agent, its first reduction potential being at least 1 V more positive than those of polycyclic aromatic hydrocarbons. C70 can also be reversibly reduced and various ions up to... 

Hydroperoxides, as optically active oxidizing agents 289-291 Hydrosulphonylation 172 /J-Hydroxyacids 619 a-Hydroxyaldehydes, synthesis of 330 a-Hydroxyalkyl acrylates, chiral 329 j -Hydroxycarboxylic esters, chiral 329 3-Hydroxycycloalkenes, synthesis of 313 Hydroxycyclopentenones, synthesis of 310 -Hydroxyesters 619 synthesis of 616 Hydroxyketones 619, 636 Hydroxymethylation 767 a-Hydroxysulphones, synthesis of 176 / -Hydroxysulphones 638, 639 reactions of 637, 944 electrochemical 1036 synthesis of 636 y-Hydroxysulphones 627 synthesis of 783... 

Figure 12-8. Principles of the chemiosmotic theory of oxidative phosphorylation. The main proton circuit is created by the coupling of oxidation in the respiratory chain to proton translocation from the inside to the outside of the membrane, driven by the respiratory chain complexes I, III, and IV, each of which acts as a protonpump. Q, ubiquinone C, cytochrome c F Fq, protein subunits which utilize energy from the proton gradient to promote phosphorylation. Uncoupling agents such as dinitrophenol allow leakage of H" across the membrane, thus collapsing the electrochemical proton gradient. Oligomycin specifically blocks conduction of H" through Fq.

Selenium is stable in water and in aqueous solutions over the entire pH interval in the absence of any oxidizing or reducing agent. Selenium can be electrochemically reduced to hydrogen selenide or to selenides that are unstable in water and aqueous solutions. It can be oxidized to selenous acid or selenites and further (electrolyti-cally) to perselenic acid (H2Se20s). Selenic and selenous acids and their salts are stable in water. The selenides, selenites, and selenates of metals other than the alkali metals are generally insoluble. 

Fujishima A, Sugiyama E, Honda K (1971) Photosensitized electrolytic oxidation of iodide ions on cadmium sulfide single crystal electrode. Bull Chem Soc Japan 44 304 Inoue T, Watanabe T, Fujishima A, Honda K, Kohayakawa K (1977) Suppression of surface dissolution of CdS photoanode by reducing agents. J Electrochem Soc 124 719-722 Elhs AB, Kaiser SW, Wrighton MS (1976) Visible light to electrical energy conversion. Stable cadmium sulfide and cadmium selenide photoelectrodes in aqueous electrolytes. J Am Chem Soc 98 1635-1637... 

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