Chemical Consequences of Single-Electron Oxidation of Phenylmesityldiazoethane

Article abstract of DOI:10.1021/ja00335a050

Both thermolysis and photolysis of 1-phenyl-2-mesityldiazoethane (PMDE) lead exclusively to products derived from facile hydrogen or mesityl migration subsequent to, or concurrent with, loss of N2.No detectable amounts of ketazine or any dimeric hydrocarbons are formed in these reactions -a result that is attributable to the steric hindrance about the diazo carbon in PMDE.Quite in contrast, the one-electron oxidation of this diazoalkane yields no monomeric products by simple hydrogen or mesityl migration; instead, ketazine and dimeric products are formed by two distinct paths.Dimerization of diazo radical cations followed by competing secondary reactions of the resulting dication is the favored path according for the major products.In a very much slower reaction, PMDE^+. attacks neutral PMDE to yield ketazine.