Abstract
Kinetic isotope effects (KIE) have been measured for oxidation reactions of ethylene by p-benzoquinone in Pd2+—MeCN—H2O—HClO4 system. Under the conditions of preferred formation of complex Pd(MeCN)(H2O)3 2+ the ratio between the initial reaction rates \(R_{{C_2}{H_4}} 0/R_{{C_2}{D_4}} 0\) is equal to 1.14±0.06 and is close to the KIE for classical chloride systems. Based on the obtained results and previous data for C2H4—C2D4 and H2O—D2O (0.97±0.12) systems, the slow step was proposed in the reaction mechanism–a trans-addition of water molecule to the cationic p-complex LPd(H2O)2(CH2CH2)2+ with formation of metalcarben-ium ion solvated by water molecule (LPd(H2O)2(CH2CH2O+H2)+).
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 0922—0923, May, 2017.
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Martynov, I.V., Efremov, G.E. & Temkin, O.N. Kinetic isotope effects in oxidation reaction of C2H4 and C2D4 by p-benzoquinone in the Pd2+—HClO4—CH3CN—H2O system. Russ Chem Bull 66, 922–923 (2017). https://doi.org/10.1007/s11172-017-1830-8
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DOI: https://doi.org/10.1007/s11172-017-1830-8