Abstract
Abstract The reaction of Na2PdCl4 with chlorine in aqueous acid solution proceeds in two stages: oxidation of the complex to a Pd(IV) species followed by a slower substitution reaction. The oxidation reaction is first order in complex and first order in chlorine. At high chloride concentration, a six-coordinate palladium(II) intermediate is formed, which is oxidised via an outer-sphere type mechanism. Oxidation of the chloroaquopalladium(II) species present at low chloride concentration occurs via a different mechanism, probably involving coordination of the oxidant in a ‘quasiinner-sphere’ mechanism.
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