Add time:08/14/2019         Source:sciencedirect.com

The cathodic reduction in DMSO solutions of six aromatic nitriles of the benzene, and eight dibenzenechromium cyano derivatives have been studied by use of the rotating disk and rotating ring-disk electrodes. A substantial change in the character of the polarization curves of π-complexes in comparison with the same cathodic reduction curves of the benzene series is observed. This change manifests itself in the disappearance of the one-electron waves in the I,E-curves and the emergence of two-electron waves. The stepwise addition of two electrons (EEC-mechanism) for free aromatic nitriles, whose anion radicals (ARs) can be reduced, is replaced by the ECE-mechanism in the nitrile complexes: the reversible transfer of the first electron is followed by the chemical decomposition reaction of anion-radicals whose products are reduced at the potential that AR is formed. The reversibility of the addition of the first electron to the free and the complexed nitriles allows their reactivity to be compared directly under cathodic conditions.

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