The solvent effect on the aquation processes of the cis-dichloro(ethylenediammine)platinum(II) using continuum solvation models

The present Letter describes a systematic analysis of the solvent effect on the hydrolysis process of an important cisplatin analogue (cis-DEP). Self-consistent reaction field continuum models were used to include the solvent effect at the HF, DFT and MP2 levels of theory. A disagreement between the gas phase calculated (k(2) = 1.92 x 10(-11) M-1 s(-1)) and experimental (k(2) = 4.4 x 10(-5) M-1 s(-1)) rate constant for the second aquation reaction of cis-DEP was recently reported by us. The value calculated in aqueous solution at the PCM-MP2 level was 2.87 x 10(-5) M-1 s(-1) in perfect accordance with experiment. Calculations using spherical cavity SCRF model require inclusion of high order multipole terms (up to octupole). (C) 2004 Elsevier B.V. All rights reserved.