Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe

The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E_1/2 = 0.55 V vs SCE), which is intermediate between the experimental ionization energies of TMPD (6.25 eV), TTF (6.83 eV), and pyrene (7.41 eV). DMAPCMe is extensively hydrogen-bonded in solution, as seen by the growth of a shifted N-H infrared vibration band. The paramagnetic resonance spectrum of the DMAPCMe⁺ radical cation matches fairly well a simulated monomer radical spectrum, but there is evidence for H-bonded paramagnetic adducts. These same adducts reduce irreversibly at 0.37 V vs SCE in acetonitrile solution.