Boundary conditions on the partitioning of deaminatively generated benzyl cations

Nitrogenous entity-separated ion pairs (NESIPs) containing benzyl cations, nitrogen gas, and pivalate anions were generated via thermal deamination of N-benzyl-N-nitrosopivalamide. Some decompositions were performed in methan olic solutions saturated with selected nucleophiles: acetate, azide, or cya nide ions. Trace amounts of benzyl cyanide and tolunitriles were observed; no corresponding products were detected in the acetate and azide cases. Oth er decompositions were performed in the absence of traditional solvent but in the presence of the nucleophilic salts; again only poor cyanide intercep tion of the cation was observed. The poor showing of the nucleophilic ions, when present, is discussed in the context of the lifetime of the cation, e ffective nucleophilicity, and cage effects in deamination.