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Hydrolysis of the amide bond in histidine- and methionine-containing dipeptides promoted by pyrazine and pyridazine palladium(II)-aqua dimers: Comparative study with platinum(II) analogues
Institution:1. University of Kragujevac, Faculty of Science, Department of Chemistry, R. Domanovi?a 12, 34000 Kragujevac, Serbia;2. Faculty of Chemistry, Adam Mickiewicz University, ul. Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland;3. Institute of Molecular Genetics and Genetic Engineering, University of Belgrade, Vojvode Stepe 444a, 11042 Belgrade, Serbia;4. Serbian Academy of Sciences and Arts, Knez Mihailova 35, 11000 Belgrade, Serbia;1. Laboratory of Inorganic Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-54124, Greece;2. Laboratory of Organic Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-54124, Greece;1. University of Kragujevac, Faculty of Science, Department of Chemistry, Radoja Domanovi?a 12, Kragujevac 34000, Serbia;2. Innovative center of the Faculty of Chemistry, Studentski trg 12-16, Belgrade 11000, Serbia;3. University of Paderborn, Department of Chemistry, Warburgertraße 100, Paderborn 33098, Germany;4. University of Montenegro, Faculty of Metalurgy and Technology, Cetinjski put bb, Podgorica 81000, Montenegro;5. University of Belgrade, Faculty of Agriculture, Department of Chemistry and Biochemistry, Nemanjina 6, Zemun-Belgrade 11080, Serbia
Abstract:Two dinuclear palladium(II) complexes, {Pd(en)Cl}2(μ-pz)](NO3)2 and {Pd(en)Cl}2(μ-pydz)](NO3)2, have been synthesized and characterized by elemental microanalysis and spectroscopic (1H and 13C NMR, IR and UV–vis) techniques (en is ethylenediamine; pz is pyrazine and pydz is pyridazine). The square planar geometry of palladium(II) metal centers in these complexes has been predicted by DFT calculations. The chlorido complexes were converted into the corresponding aqua complexes, {Pd(en)(H2O)}2(μ-pz)]4+ and {Pd(en)(H2O)}2(μ-pydz)]4+, and their reactions with N-acetylated l-histidylglycine (Ac–l–His–Gly) and l-methionylglycine (Ac–l–Met–Gly) were studied by 1H NMR spectroscopy. The palladium(II)-aqua complexes and dipeptides were reacted in 1:1 M ratio, and all reactions performed in the pH range 2.0 < pH < 2.5 in D2O solvent and at 37 °C. In the reactions of these complexes with Ac–l–His–Gly and Ac–l–Met–Gly dipeptides, the hydrolysis of the amide bonds involving the carboxylic group of both histidine and methionine amino acids occurs. The catalytic activities of the palladium(II)-aqua complexes were compared with those previously reported in the literature for the analogues platinum(II)-aqua complexes, {Pt(en)(H2O)}2(μ-pz)]4+ and {Pt(en)(H2O)}2(μ-pydz)]4+.
Keywords:Dinuclear palladium(II) complexes  Methionine- and histidine-containing dipeptides  NMR spectroscopy  Hydrolysis
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