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Arenediazonium ions are strong oxidizing agents that in the presence of suitable electron donors readily participate in electron transfer reactions. These redox reactions have attracted considerable interest because of the well-known mutagenic and carcinogenic capacity of the ions themselves or the other species derived from their dediazoniation processes, which is related to their ability to form aryl radicals via one-electron processes. Aromatic diazonium salts are also as important in preparative and synthetic chemistry and in many industrial procedures.
The release of an electron to an arenediazonium salt may be accomplished in several ways, but the most direct one is the reduction of the arenediazonium salt at the surface of an electrode and thus they are susceptible to detection based on the reduction on a suitable type of electrode. The knowledge of the mechanism of their electrode reactions can provide us with useful clues to elucidate their reaction mechanisms, especially those involving electron transfer processes. Undoubtedly, the measurement of the electrochemical response of electroactive compounds is essential in fully understanding the role of electron donors, the role of the solvent and the role of added electrolytes, inorganic or organic compounds in electron transfer reactions since organic radical intermediates in biological systems could be specifically stabilized in some suitable microscopic environments.
The use of modern electrochemical methods such as differential pulse polarography (DPP), differential pulse voltammetry (DPV) and cyclic voltammetry (CV) may play an important role when investigating arenediazonium chemistry, specially in complex matrix such as colloids or in biological fluids, providing an independent alternative way to detect and to investigate arenediazonium chemistry. The present review is aimed to summarize research on the applications of electrochemical behavior of arenediazonium ions and on the applications of electrochemical methods to investigate their reactions mechanisms. Other important applications such as the electrochemical reduction of arenediazonium salts as a means for functionalizing carbon surfaces will be also mentioned.