Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe
- 15 October 1987
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 87 (8) , 4967-4971
- https://doi.org/10.1063/1.452810
Abstract
The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E1/2=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.Keywords
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