Redox approach

The vast majority of early amine racemizations involve an oxidation-reduction approach, with the oxidation of the amine center removing the chirality so that subsequent reduction yields the racemate. The most efficient redox approach is achieved when the oxidized and reduced forms of the substrate are in equilibrium... 

Figure 9.14 Modified redox approach for the synthesis of menadione [75].

Various mechanistic-based kinetic models that describe the effect of NO2 have appeared in the hterature. Here we attempt to summarize the current understanding of the mechanism and associated kinetics. As before, we consider both the LH and Redox approaches. 

Processes that have been studied with different redox approaches include ... 

A number of Ge-S polymers (102) have been made using the redox approach of Kobayashi and co-workers (Scheme 31). It is interest that the reaction with sulfides occurs without the use of a catalyst, dehydrating agent, or acid scavenger. 

In 2011, Bode et al. reported a unique dual-catalysis redox approach to the KR of secondary amines based on the catalytic generation of an acyl azolium species [132]. Indeed, these species, which can undergo rapid acyl transfer in the presence of various nucleophiles such as water, alcohols, or thiols, are absolutely inert in the presence of amines except if an additive such as imidazole or l-hydroxy-7-azabenzotriazole (HOAt) is added to the reaction mixture [133]. 

One of the most important applications of redox titrimetry is in evaluating the chlorination of public water supplies. In Method 9.3 an approach for determining the total chlorine residual was described in which the oxidizing power of chlorine is used to oxidize R to 13 . The amount of 13 formed is determined by a back titration with 8203 . 

In the reprocessing environment there are many mthenium compounds, some of which are gaseous. Some reprocessing approaches, notably the REDOX process, require a mthenium removal step in the off-gas system. The PUREX process maintains mthenium in one of its nonvolatile states. 

Many experimental approaches have been appHed to the deterrnination of stabihty constants. Techniques include pH titrations, ion exchange, spectrophotometry, measurement of redox potentials, polarimetry, conductometric titrations, solubiUty deterrninations, and biological assay. Details of these methods can be found in the Hterature (9,10). 

A useful approach to the substitution of ring C—H positions lies in the activation of the heteroaromatic system by an A-oxide group, initiating a formal intramolecular redox reaction. 1-Methyllumazine 5-oxide reacts with acetic anhydride in a Katada rearrangement... 

The holistic thermodynamic approach based on material (charge, concentration and electron) balances is a firm and valuable tool for a choice of the best a priori conditions of chemical analyses performed in electrolytic systems. Such an approach has been already presented in a series of papers issued in recent years, see [1-4] and references cited therein. In this communication, the approach will be exemplified with electrolytic systems, with special emphasis put on the complex systems where all particular types (acid-base, redox, complexation and precipitation) of chemical equilibria occur in parallel and/or sequentially. All attainable physicochemical knowledge can be involved in calculations and none simplifying assumptions are needed. All analytical prescriptions can be followed. The approach enables all possible (from thermodynamic viewpoint) reactions to be included and all effects resulting from activation barrier(s) and incomplete set of equilibrium data presumed can be tested. The problems involved are presented on some examples of analytical systems considered lately, concerning potentiometric titrations in complex titrand + titrant systems. All calculations were done with use of iterative computer programs MATLAB and DELPHI. 

The calculation of E] and X from computational methods is the focus here. Generally, the energetics of these quantities are separated into contributions from the inner and outer shells. For transfer between small molecules, the inner shell generally is defined as the entire solutes A and D, and the outer shell is generally defined as only the solvent. However, in a more practical approach for proteins, the inner shell is defined as only the redox site, which consists of the metal plus its ligands no further than atoms of the side chains that are directly coordinated to the metal, and the outer shell is defined as the rest of the protein plus the surrounding solvent. Thus... 

The combination of hard (A) and soft (5) coordination in the 1,5-P2N4S2 ring system leads to a diversity of coordination modes in complexes with transition metals (Lig. 13.1). In some cases these complexes may be prepared by the reaction of the dianion [Ph4P2N4S2] with a metal halide complex, but these reactions frequently result in redox to regenerate 13.3 (L = S, R = Ph). A more versatile approach is the oxidative addition of the neutral ligand 13.3 (L = S) to the metal centre. 

Electron-hopping is the main charge-transport mechanism in ECHB materials. There is precedence in the photoconductivity Held for improved charge transport by incorporating a number of redox sites into the same molecule. A number of attempts to adapt this approach for ECHB materials have been documented. Many use the oxadiazole core as the electron-transport moiety and examples include radialene 40 and dendrimer 41. However, these newer systems do not offer significant improvements in electron injection over the parent PBD. 

Empirical approach to ligand effects on the kinetics of substitution and redox reactions. V. Gut-mann and R. Schmid, Coord. Chem. Rev., 1974,12, 263-293 (90). 

The donor-acceptor approach to solvent effects on the rates of redox reactions between different metal complexes, R. Schmid, Rev. Inorg. Chem., 1979,1,117-131 (48). 

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