Short Communication: Kinetic Study of the Interactions of Palladium(II) Complexes with Thiols in Acidic Aqueous Solution
AUSTRALIAN JOURNAL OF CHEMISTRY（2001）
Abstract
The kinetics of complex formation between the monofunctional palladium(II) complexes [Pd(dien)Cl](+) and [Pd(gly-met-S,N,N')Cl], where (dien) is diethylentriamine and (gly-met) is glycyl-L-methionine, and L-cysteine, DL-penicillamine and glutathione were studied in an aqueous 0.10 mol dm(-3) perchloric acid medium by using variable-temperature stopped-flow spectrophotometry. Second-order rate constants, k(2)(298), varied between 17.02 and 1.44x10(3) M-1 s(-1). Higher reactivity was observed for the [Pd( dien) Cl](+) complex, whereas glutathione was found to be the strongest nucleophile. The reactivity of the thiol nucleophile follows the sequence DL-penicillamine < L-cysteine < glutathione. However, the variation in size, bulk and solvation of the entering thiols reflects their properties as nucleophiles. Negative entropies of activation support a strong contribution from bond making in the transition state of the process.
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Key words
crystal structures,ab initio calculations,combinatorial chemistry,analytical chemistry,structure,biocatalysis,density functional theory,enzymes,combinatorial,medicinal chemistry,kinetics,self assembly,inorganic chemistry,interfaces,ionic liquids,sensors,catalysis,spectroscopy,mass spectrometry,reaction mechanisms,photochemistry,biosensors,amino acids,educational,nanotechnology,quantum chemistry,colloids,peptide,green chemistry,pharmaceutical chemistry,supramolecular chemistry,surface chemistry,organic chemistry,crystallography,electrochemistry,polymer chemistry,proteins,computational chemistry,physical chemistry,biological chemistry,macromolecules
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