The Nature of Azo-Substituted Carbocations: N-N π-Electron Stabilization versus Nitrogen Nonbonding Electron Stabilization.

Computational and experimental studies reveal two different modes of cation stabilization by the phenylazo group. The first mode involves a relatively weak conjugative interaction with the azo π-bond, while the second mode involves an interaction with the nitrogen nonbonding electrons. The 4-phenylazo group is slightly rate-retarding in the solvolysis of cumyl chloride and benzyl mesylate derivatives but rate-enhancing in the solvolysis of α-CF benzylic analogs. The phenylazo group can become a potent electron-donating group in cations such as [MeC─N═N─Ph]. Nonbonding electron stabilization can be strong enough to offset the very powerful γ-silyl stabilization. In aromatic cyclopropenium and tropylium cations, the demand for stabilization is quite low, and the mode of phenylazo stabilization reverts back to the less-effective π-stabilization. The solvolysis of -4-phenylazo benzyl mesylate is faster than that of -4-phenylazo benzyl mesylate. Products formed suggest a stepwise ionization, cation isomerization, and nucleophile capture mechanism. Computational studies indicate a vanishingly small barrier for the isomerization of the -cation intermediate to the -cation.