Dimerization of organic free radicals in solution. 1. Temperature dependent measurements.

Dimerization enthalpies and equilibrium constants have been determined for the radical anion of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), the radical cations of N,N,N',N'-tetramethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, N,N,N',N'-tetraethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine and N,N,N'-trimethyl-p-phenylenediamine. Neutral radicals investigated are 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and galvinoxyl. Solvent used was acetone, EtOH/Et2O-mixture (2:1 volume), propionitrile/butyronitrile-mixture (1:1 M) and dichloromethane. Measured dimerization enthalpies deltaHdim vary from -72.1 to -16.6 k/mol.