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Kinetic isotope effects for oxidation reaction of olefins by p-quinones in water-acetonitrile solutions of cationic and chloride anionic palladium complexes
Authors:D S Zakharova  O A Chertkova  A A Chelkin  L G Bruk  O N Temkin
Institution:1. M. V. Lomonosov Moscow State University of Fine Chemical Technologies, 86 prosp. Vernadskogo, 119571, Moscow, Russian Federation
Abstract:Kinetic isotope effects for oxidation reactions of ethylene and cyclohexene in solutions of cationic palladium(ii) complexes in MeCN-H2O(D2O) systems, were measured. It was established that the ratio of the initial reaction rates ${{R_0^{H_2 O} } \mathord{\left/ {\vphantom {{R_0^{H_2 O} } {R_0^{D_2 O} }}} \right. \kern-0em} {R_0^{D_2 O} }} $ is equal to 1 for both reactions with the use of cationic complexes of the type Pd(MeCN) x (H2O)4?x 2+, which differs from oxidation reactions catalyzed by chloride palladium complexes in the same solutions, where the ratio ${{R_0^{H_2 O} } \mathord{\left/ {\vphantom {{R_0^{H_2 O} } {R_0^{D_2 O} }}} \right. \kern-0em} {R_0^{D_2 O} }} $ = 5.0±0.16 and 4.73±0.14 at H+ molar fraction of 0.48 and 0.16, respectively (H+ molar fraction was calculated based on the sum of H+] and D+]).
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