Dediazoniation of Arenediazonium Ions in Homogeneous Solution. Part XII. Solvent effects in competitive heterolytic and homolytic dediazoniations

Abstract In heterolytic dediazoniations arenediazonium salts form aryl cations. The reaction rates are relatively slow; they depend only to a small extent on the solvent. It is shown that the solvents in which the heterolytic dediazoniation mechanism is predominant have a low nucleophilicity, whereas in solvents of high nucleophilicity homolysis of arenediazonium salts, i.e. the formation of aryl radicals and related intermediates, is favoured. Under comparable conditions, homolytic rates are faster than the corresponding rates of heterolysis. Homolysis is strongly enhanced by addition of nucleophiles which form relatively stable radicals by electron transfer. The ability of additives to catalyze homolysis of arenediazonium salts can be explained using the concept of a nucleofugic In the original proposal [32] we used the word nucleofugal. In keeping with a forthcoming proposal on nomenclature in physical organic chemistry by Commission III.2 (Physical Organic Chemistry) of IUPAC we now use the word nucleofugic. homolytic leaving group.