Inorganic Chemistry, Vol.36, No.7, 1454-1463, 1997
Complex-Formation and Ligand Substitution-Reactions of (2-Picolylamine)Palladium(II) with Various Biologically Relevant Ligands - Characterization of (2-Picolylamine)(1,1-Cyclobutanedicarboxylato)Palladium(II)
The influence of a 2-picolylamine (pie) ligand on the reactivity of Pd(TI) complexes was investigated by detailed equilibrium and kinetic studies. Reactions of [Pd(pic)(H2O)(2)](2+) with chloride, 1,1 -cyclobutanedicarboxylic acid (CBDCAH(2)), inosine (ino), and inosine 5’-monophosphate (5’-IMP) were studied. A significantly higher reactivity for the first reaction step involving the displacement of one coordinated solvent molecule on [Pd(pic)(H2O)(2)](2+) was observed for the nucleoside inosine (k(10 degrees C) = 25 400 +/- 200 M(-1) s(-1)) than for the nucleotide 5’-IMP (k(10 degrees C) = 7100 +/- 300 M(-1) s(-1)) and for CBDCAH(-) (k(25 degrees C) = 5380 +/- 70 M(-1) S-1; Delta H double dagger = 54 +/- 2 kJ mol(-1); Delta S double dagger = 10 +/- 4 J K-1 mol(-1); Delta V double dagger = -0.2 +/- 0.7 cm(3) mol(-1)). The results are compared and discussed in reference to data reported for closely related systems in the literature. The molecular structure of [Pd(pic)(CBDCA)1 in solution and in the solid state was resolved. [Pd(pic)(CBDCA)]. 2H(2)O crystallizes in the space group P2(1)/c (monoclinic,a = 5.659(5) Angstrom, b = 18.320(5) Angstrom, c = 14.027(5) Angstrom, beta = 97.748(5)degrees, V = 1440.94(14) Angstrom(3), Z = 4).
Keywords:AQUEOUS-SOLUTION;INOSINE 5’-MONOPHOSPHATE;FORMATION KINETICS;EQUILIBRIUM DATA;MECHANISM;PLATINUM(II);NUCLEOSIDES;CISPLATIN;DIAQUA(ETHYLENEDIAMINE)PALLADIUM(II);PALLADIUM(II)