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Kinetics and mechanism of the substitution reactions of some bifunctional palladium(II) complexes with different nitrogen-donor heterocycles

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Abstract

Substitution reactions of three Pd(II) complexes, [Pd(cbdca)Cl2]2− (cbdca = cyclobutane-1,1-dicarboxylato), [Pd(ox)Cl2]2− (ox = oxalato) and [Pd(mal)Cl2]2− (mal = malonato), with different five- and six-membered N-heterocycles, such as pyrazole, 3-amino-4-iodo-pyrazole (pzI), 5-amino-4-bromo-3-methyl-pyrazole (pzBr), 1,2,4-triazole, pyrazine, imidazole, pyridazine and pyrimidine, were investigated in aqueous 0.10 M NaClO4 with the presence of 20 mM NaCl using variable-temperature stopped-flow spectrophotometry. Substitution of these complexes occurs in two consecutive reversible steps, and their reactivity decreases in order [Pd(cbdca)Cl2]2− > [Pd(mal)Cl2]2− > [Pd(ox)Cl2]2−. The most reactive nucleophile among the five-membered heterocycles is imidazole, while pyridazine is the most reactive among the six-membered heterocycles. Activation parameters were determined for all reactions, and negative values for entropy of activation, ΔS≠, support an associative mode of substitution. The reaction between [Pd(mal)Cl2]2− complex and pzBr was investigated by 1H NMR, and the obtained results confirm that substitution with nitrogen-donor nucleophile does not lead to decomposition of the complex.

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Acknowledgments

The authors gratefully acknowledge financial support from the Ministry of Education, Science and Technological Development of the Republic of Serbia, Project No. 172011.

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Authors and Affiliations

  1. Faculty of Metallurgy and Technology, University of Montenegro, Cetinski put, 81000, Podgorica, Montenegro

    Milica Kosović & Željko Jaćimović

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

    Živadin D. Bugarčić & Biljana V. Petrović

Authors
  1. Milica Kosović
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  2. Željko Jaćimović
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  3. Živadin D. Bugarčić
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  4. Biljana V. Petrović
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Correspondence to Biljana V. Petrović.

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Kosović, M., Jaćimović, Ž., Bugarčić, Ž.D. et al. Kinetics and mechanism of the substitution reactions of some bifunctional palladium(II) complexes with different nitrogen-donor heterocycles. Transition Met Chem 41, 161–168 (2016). https://doi.org/10.1007/s11243-015-0008-1

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