Hydration process as an activation of trans‐ and cisplatin complexes in anticancer treatment. DFT and ab initio computational study of thermodynamic and kinetic parameters

The thermodynamic and kinetic aspects of hydration reactions of cis‐/transplatin were explored. The polarizable continuum model was used for estimation of solvent effects. Using the B3LYP/6‐31+G(d) method, the structures were optimized and vibrational frequencies estimated. Interaction energies and activation barriers were determined at the CCSD(T)/6‐31++G(d,p) level within the COSMO approach. An associative mechanism was assumed with a trigonal‐bipyramidal structure of the transition state. Within the applied model, all the hydration reactions are slightly endothermic. The Gibbs energies of cisplatin hydration amount to 7.0 and 14.2 kcal/mol for the chloride and ammonium replacement, respectively. Analogous values for the transplatin reactions are 6.8 and 11.9 kcal/mol. The determined rate constants are by several (three to four) orders of magnitude larger for the dechlorination process than for deammination. The cisplatin dechlorination rate constant was established as 1.3 · 10−4 s−1 in excellent accord with the experiment. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 907–914, 2005

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