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Kinetics, mechanism and density functional theory calculations on base hydrolysis of α-amino acid esters catalyzed by [Pd(AEMP)(H2O)2]2+ (AEMP = 2-(2-aminoethyl)-1-methylpyrrolidine)

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Abstract

Pd(AEMP)Cl2 (AEMP = 2-(2-aminoethyl)-1-methylpyrrolidine) was synthesized and characterized by spectral and thermal measurements.[Pd(AEMP)(H2O)2]2+ reacts with amino acid esters (L) to form mixed ligand [Pd(AEMP)L]2+ complexes. The kinetics of the base hydrolysis of [Pd(AEMP)L]2+ was studied by a pH-stat technique and the corresponding rate constants are reported. The coordinated glycine methyl ester is hydrolyzed efficiently, whereas the coordinated methionine- and histidine- methyl esters undergo hydrolysis with a much lower catalytic activity. The catalytic effect is controlled by the mode of coordination of the ester to the Pd(II) complex. Possible mechanisms for these reactions are considered. Activation parameters were determined experimentally for the hydrolysis of the coordinated glycine methyl ester. DFT calculations (B3LYP/def2svp) were applied to gain further insight into the possible mechanism of the base hydrolysis of the amino acid esters. The calculations are discussed in reference to the reported experimental data.

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Acknowledgements

D.C. thanks the Ministry of Education, Science and Technological Development of the Republic of Serbia (Project No. 172011) and the European Union for an Erasmus + Fellowship. The authors gratefully acknowledge the Regionales Rechenzentrum Erlangen (RRZE) for a generous allotment of computer time. We like to thank Prof. Tim Clark for hosting this work at the CCC.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Cairo University, Giza, Egypt

    Mohamed M. Shoukry, Mohamed R. Shehata & Mona S. Ragab

  2. Department of Chemistry, Faculty of Science, Islamic University, Al-Madinah, Saudi Arabia

    Mohamed M. Shoukry

  3. Department of Chemistry, Faculty of Science, University of Kragujevac, Radoja Domanovića 12, P. O. Box 60, 34000, Kragujevac, Serbia

    Dušan Ćorćić

  4. Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Egerlandstr. 1, 91058, Erlangen, Germany

    Dušan Ćorćić, Ralph Puchta & Rudi van Eldik

  5. Department of Chemistry and Pharmacy, Computer Chemistry Center, University of Erlangen-Nuremberg, Nägelsbachstr. 25, 91052, Erlangen, Germany

    Ralph Puchta

  6. Central Institute for Scientific Computing (ZISC), University of Erlangen-Nuremberg, Martensstr. 5a, 91058, Erlangen, Germany

    Dušan Ćorćić & Ralph Puchta

  7. Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387, Kraków, Poland

    Rudi van Eldik

  8. Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100, Toruń, Poland

    Rudi van Eldik

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Shoukry, M.M., Shehata, M.R., Ragab, M.S. et al. Kinetics, mechanism and density functional theory calculations on base hydrolysis of α-amino acid esters catalyzed by [Pd(AEMP)(H2O)2]2+ (AEMP = 2-(2-aminoethyl)-1-methylpyrrolidine). Reac Kinet Mech Cat 129, 613–626 (2020). https://doi.org/10.1007/s11144-020-01734-7

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