cis-Diazenes. Viscosity Effects, One-Bond Scission, and Cis-Trans Isomerization

Article abstract of DOI:10.1021/jo00296a026

Effects of solvent viscosity on the rates of overall thermal decomposition, deazatization, and iomerization of several symmetric and unsymmetric cis-diazenes (cis-azoalkanes) have been determined in pure alkanes and mixtures of octane and mineral oil.Increasing viscosity decreases the overall decomposition and deazatization rates for all of these cis-diazenes.While isomerization rates also decrease with increasing viscosity for most of the diazenes, that for cis-N-tert-butyl-N'-1-norbornyldiazene (1) increases.These results are interpreted in terms of deazatization via one-bond scission and an intermediate diazenyl radical, isomerization via nonradical inversion, and the possibility of isomerization via a diazenyl radical for 1.