Effect of steric hindrance on kinetic and equilibrium data for substitution reactions of diaqua(N-substituted ethylenediamine)palladium(II) with chloride in aqueous solution
作者:H. Hohmann、B. Hellquist、R. van Eldik
DOI:10.1016/s0020-1693(00)80912-3
日期:1991.10
Abstract Kinetic and thermodynamic data are reported for the complex formation reactions: Pd(R4en)(H2O)22+Cl− Pd(R4en)(H2O)Cl++H2O and Pd(R4en)(H2O)Cl++Cl− Pd(R4en)Cl2+H2O, as a function of steric hindrance for RMe and Et. The reported rate constants for these reactions decrease drastically on increasing the steric hindrance. These findings along with strongly negative △S≠ values support the operation
Mechanistic information on the reaction of model palladium(II) complexes with purine nucleosides and 5′-nucleotides in reference to the antitumor activity of related platinum complexes
作者:M. Shoukry、H. Hohmann、R. van Eldik
DOI:10.1016/s0020-1693(00)92360-0
日期:1992.8
The reaction of Pd(Me,en)Cl2 (Me4en=NNN',N'-tetramethylethylenediamine) with inosine and 5'-inosine monophosphate was studied as a function of chloride concentration and pH. Evidence for the formation of a 1:1 complex with these nucleophiles is presented, and the kinetic data indicate that Pd(Me4en)(Cl)H2O+ is the only reactive species under the selected experimental conditions. The results are compared to earlier data for the reactions of Pd(R4en)(H2O)22+ (R = H, Me, Et) with a series of nucleosides and 5'-nucleotides. The dependencies studied in this investigation allow some tentative extrapolations to conditions relevant for the antitumor activity of related Pt(II) complexes.