Kinetics of substitution of aqua ligands from cis-diaqua(ethylenediamine)platinum(II) perchlorate by DL-penicillamine in aqueous medium

The kinetics of the interaction of DL-penicillamine with [Pt(en)(H2O)(2)](2+) have been studied spectrophotometrically as a function of [Pt(en)(H2O)(2)](2+), [DL-penicillamine] and temperature at pH 4.0. The reaction proceeds via rapid outer sphere association complex formation, followed by two slow consecutive steps. The first is the conversion of the aforementioned complex into the inner sphere complex and the second is the slower chelation step whereby another aqua ligand is replaced. The association equilibrium constant (K-E) for the outer sphere complex formation has been evaluated together with rate constants for the two subsequent steps. Activation parameters have been calculated for both steps using the Eyring equation (DeltaH(1)(double dagger) = 46.5 +/- 5.0 kJ mol(-1), DeltaS(1)(double dagger) = - 143.0 +/- 15.0 J K-1 mol(-1), DeltaH(2)(double dagger) = 44.3 +/- 1.3 kJ mol(-1), DeltaS(2)(double dagger) = -189.0 +/- 4.2 J K-1 mol(-1)). The low enthalpy of activation and large negative entropy of activation values indicate an associative mode of activation for both aqua ligand substitution processes.