Practical applications and unique kinetic phenomena have generated consider
able interest in the redox chemistry of chlorine(III). The complex kinetic
and stoichiometric features of the related reactions are well documented, b
ut relatively little is known about possible interactions between chlorine(
III) and transition metal ions, Recent studies confirmed that the chlorite
ion forms weak complexes with common metal ions such as Cu(II), Fe(III) or
Hg(II) and the formation of an inert chlorito complex was also reported. Th
is paper reviews kinetic and equilibrium aspects of the formation of chlori
to complexes as well as the role of transition metal ions in the redox reac
tions and the catalytic decomposition of chlorine(III). It will be shown th
at the metal ions enhance the reactivity of chlorine(III) by activating the
O-Cl bond. Chlorito complexes may undergo either redox decomposition or pr
omote the reactions of the coordinated chlorine(III) with other oxychlorine
species. It is a common feature that reactive intermediates are formed, wh
ich are involved in subsequent fast reactions with the reactants and other
intermediates. As a consequence, complex kinetic patterns ensue and the sto
ichiometries are kinetically controlled. Mechanistic aspects of these react
ions will be discussed in detail. (C) 2001 Elsevier Science B.V. All rights
reserved.