The Decarbonylation of the Acetamide Radical Cation and the Enolization of its Dimer by Self-Catalysis

The acetamide radical cation, CH 3 C(=O)NH 2 •+ , and its enol, CH 2 =C(OH)NH 2 •+ , undergo several unimolecular reactions in the μs time-frame of which decarbonylation is predominant. This reaction produces the ylid ion CH 2 NH 3 •+ , rather than CH 3 NH 3 •+ [ J. Am. Chem. Soc. 109, 4819 (1987)]. A previously proposed mechanism via ion–dipole complexes is confirmed by the present CBS-QB3 calculations. These calculations reveal the existence …