Electrochemical structural relationships

Because of the precise control of the redox steps by means of the electrode potential and the facile measurement of the kinetics through the current, the electrochemical approach to. S rn I reactions is particularly well suited to assessing the validity of the. S rn I mechanism and identifying the side reactions (termination steps of the chain process). It also allows full kinetic characterization of the reaction sequence. The two key steps of the reaction are the cleavage of the initial anion radical, ArX -, and conversely, formation of the product anion radical, ArNu -. Modeling these reactions as concerted intramolecular electron transfer/bond-breaking and bond-forming processes, respectively, allows the establishment of reactivity-structure relationships as shown in Section 3.5. 

C. A. Lucas and N. M. Markovic. Structure relationships in electrochemical reactions. In Encyclopedia of electrochemistry, vol. 2, ed. A. J. Bard, M. Stratmann, and E. J. Calvo. Interfacial kinetics and mass transport. Weinheim, Germany Wiley-VCH, 2003. 

Redox potential-electronic structure relationships in 18-and 17-electron mononitrUe complexes of Re have been established. It was possible to estimate, for the nitrile and related ligands, for example, in complexes (3-6), the values of the electrochemical Pl ligand parameter, a measure of the net electron donor minus itt-acceptor character of a ligand. The... 

The nature of organic pollutant influences strongly the EOI values. In this paper the influence of benzene derivatives on the EOI value has been studied using a Pt anode. Effort has been made to treat the experimental EOI data by correlation analysis [the term "Quantitative Structure - Electrochemical Activity Relationship" (QSEAR) was used for this approach] using the equation... 

Redox potential-structure relationships in metal complexes. Part 3. The electrochemical activation of co-ordinated hydrazido(2-)-ligands J.Chem.Soc. Dalton Trans., (1981), 419-424... 

---