Catalysis homogeneous redox

Cyclic voltammetric responses corresponding to the simple catalytic scheme in Figure 4.1 and to more complex schemes were discussed in detail in Section 2.2.6. The parameters that control the catalytic current have been identified and their effects quantified. Applications of homogeneous redox catalysis to the characterization of short-lived intermediates and the determination of their redox properties have been discussed in Sections 2.3 and 2.6.4. 

The reduction of organic halides in the presence of aromatic hydrocarbons, the subject of detailed kinetic studies, provide rate constants for the homogeneous ET [147-150] and the follow-up reaction [151]. The theoretical basis for this kind of experiment ( homogeneous redox catalysis ) was laid by Saveant s group in a series of papers during the years 1978-80 [152-157]. Homogeneous ET also plays an important role in the protonation of anion radicals [158]. 

Radical-anion complexes Scope of this review 91 Thermodynamic and kinetic methodologies Voltammetric methods 92 Homogeneous redox catalysis 94 Convolution analysis 98 Laser flash photolysis 102 Photoacoustic calorimetry 103 Thermochemical estimates 105 Fleduction of C—O and O O bonds 106 Reduction of ethers 107 Reduction of peroxides and endoperoxides Reduction of S—S and C—S bonds 136 Reduction of disulfides 137 Reduction of sulfides 150 Concluding remarks 157 Fleferences 160... 

Fig. 5 Typical normalized voltammetric curves for homogeneous redox catalysis. The figure shows experimental data for the catalytic of reduction of DTBP by anthracene (ImM in DMF/O.IM TEAP at 25°C). The voltammetric curves were obtained, from left to right, at scan rates of 0.02, 0.05, 0.1 and 0.2 Vs . respectively. The concentrations of DTBP are, from bottom to top (a) = 0. (b)==1.0, and (c) = 2.0mM. All currents are normalized to...

The reduction of benzyl aryl ethers has been thoroughly investigated by voltammetric reduction, homogeneous redox catalysis,and currently, by convolution analysis. A family of ethers activated by proper substitution on the phenoxy side were chosen to provide a wide variation in the ET and bond cleavage properties of the molecule. ... 

The methods for the theoretical treatment of the homogeneous redox catalysis have been mainly developed by Saveant et al. These methods allow to calculate the lifetimes of short-lived anion radicals and the standard potentials of the substrates from redox-catalytic experiments which are directly not accessible... 

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