Air-persistent monomeric (amino)(carboxy) radicals derived from cyclic (alkyl)(amino) carbenes

A series of monomeric (amino)(carboxy) radicals featuring carbonyl substituents with increasing electron-withdrawing properties (3a, phenyl; 3b, 3,5-bis(trifluoromethyl)phenyl; 3c, perfluorophenyl; 3d, heptafluoropropyl; 3e, 2H-pyrroliumyl) were synthesized in two or three steps from stable cyclic (alky)(amino)carbenes (CAACs). Although (amino)(carboxy) radicals had been previously considered as highly air-sensitive, some of these compounds feature half-lives of hours (3d), and even days (3c and 3e) in well-aerated solutions. DFT calculations show that (amino)(carboxy) radicals evolve from C-centered radical to ambidentate C,O-radicals when increasing the electron-withdrawing properties of the carbonyl substituent. This is paralleled with a destabilization of the peroxide resulting from the addition of dioxygen to the radical. This latter reaction is even predicted to be endothermic for substituents with Hammett constant σp > 0.2.