Structure-resonance theory and electrochemical oxidation potentials of π-electron hydrocarbons

✍ Scribed by A.S. Shawali; W.C. Herndon; C. Párkányi

• Publisher: Elsevier Science
• Year: 1982
• Tongue: English
• Weight: 369 KB
• Volume: 27
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(82)80202-8

✦ Synopsis

The polarographic half-wave oxidation potentials of 51 benzenoid hydrocarbons are correlated with the logarithms of the structure counts of the neutral molecule and the radical cation, in SCR and In SC,? > respectively. For example, for 25 unsubstituted hydrocarbons and 26 methylsubstituted hydcocarbons, the following relationship was obtained: E,,, (ox) = 4.018 + 1.607 InSC, -1.027 In SC,.; r = 0.955, s = k 0.07. Such an excellent correlation indicates that effects associated with delocalization of zelectronsand the n-electron charge distribution in the neutral and charged molecular species, respectively. are significant in electrochemical oxidation, contrary to an earlier literature report which claimed that they are not. The results aIso show that the structure counts provide a simple working method for correlations of the electrochemical reactivities of polynuclear aromatic hydrocarbons and their derivatives.