Complex formation between chlorine dioxide and 2,2,6,6-tetramethylpiperidin
e-1-oxyl (TEMPO) and its thermodynamic characteristics were studied in a nu
mber of organic solvents. The complex was shown to transform into the oxoam
monium salt. The kinetics of this reaction were studied, and the equilibriu
m constants of the TEMPO . ClO2 complex, determined by direct measurements
and from kinetic data, were found to be in good agreement. The electronic s
tructure of the complex is discussed in the light of recent theoretical res
ults. Copyright (C) 2000 John Wiley & Sons, Ltd.