Abstract
The rate constants of deuterium exchange for cyclohexane in CH3COOD/D2O have been measured in the presence of 12 complexes of Pt(II) with various ligands (Cl, H2O, NH3, Br, NO2, py, DMSO, PPh3, etc.). The change in the rate constant is shown to follow the reverse series of the trans-effect of Pt(II) ligands. The rate constant of the interaction of PtCl2Sn (S is H2O, CH3COOH, n=1, 2) with cyclohexane in CH3COOD/D2O (1∶1), k, equals 2.5×108 exp (−18200/RT) 1 mol−1 sec−1 (at 354–385 K). The ratio of rate constants for PtCl2S2, PtCl3S− and PtCl 2−4 is 100∶6∶0.5 at 100°C.
Abstract
Измерены константы скорости дейтерообмена циклогексана в среде CH3COOD−D2O при катализе 12-ю комплексами Pt(II) с различными лигандами (Cl, H2O, NH3, Br, NO2, ру, DMCO, PPh3 и др.). Показано, что изменение константы скорости следует обратному ряду трансэффекта лигандов у Pt(II). Для комплекса PtCl2Sn (S−H2O, CH3COOH, n=1,2) константа скорости взаимодействия его с циклогексаном в 1∶1 CH3COOD−D2O k=2,5·108 exp(−18200/RT)л. моль−1 сек−1 (354–385°К). Константы скорости при 100°C для PtCl2S2, PtCl3S− и PtCl 2−4 относятся между собой как 100∶6∶0,5.
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Gol'dshleger, N.F., Shteinman, A.A. Pt(II) complexes in activation of saturated hydrocarbons. React Kinet Catal Lett 6, 43–50 (1977). https://doi.org/10.1007/BF02067738
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DOI: https://doi.org/10.1007/BF02067738