[Zurück]

A. Samanta, I. Mitra, S. Mukherjee, P Reddy, S. Mahata, G. Ghosh, B. Misini, W. Linert, S. Moi, A. Karmakar:
"Third order kinetics for interaction of glutathione with dinuclear Pd(II) complex and their mechanism, DNA binding and DFT study";
Journal of Solution Chemistry, 47 (2018), S. 1139 - 1156.

A kinetics and mechanistic study of the interaction between the bridged dimer [Pd(pic)(OH)]2+ 2 (where pic = 2-aminomethylpyridine) and glutathione (GSH) has been performed under pseudo-first order conditions using a stopped-flow spectrophotometer. The reaction follows a distinctive third-order kinetics via two consecutive steps. The first step follows the rate law kobs = k1[GSH]2, whereas step two is independent of the GSH concentration. The activation parameters, ΔH# and ΔS# for both steps, were determined and an associative mode of activation is suggested for the substitution process. Geometry optimizations and HOMO-LUMO energy calculations were done by DFT. The UV spectra of the complexes were compared with theoretically obtained TD-DFT spectra. Complex 2 and 3 interact non-covalently with calf-thymus DNA with binding constants (Kb and KSV) of the order of 104 L·mol−1.

Kinetics and mechanism · Third order reaction · Di-μ-hydroxo Pd(II) dimer · TD-DFT · DNA binding

http://dx.doi.org/10.1007/s10953-018-0783-3