Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands
Само за регистроване кориснике
2014
Аутори
Begović, NebojšaBlagojević, Vladimir A.
Ostojić, Sanja B.
Micić, Darko M.
Filipović, Nenad R.
Anđelković, Katarina K.
Minić, Dragica M.
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Thermal stability of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands was investigated using a combination of experimental measurements and DFT calculations. All complexes exhibit a reversible second-order transition around 333 K, which can be attributed to structural reorganization of the ligand molecules. Thermal degradation begins in 570-610 K temperature region, with an endothermic peak, followed by exothermic peaks in DSC. TG measurements show a well-defined mass loss corresponding to the initial degradation, while subsequent processes are poorly separated. DFT calculations suggest that the initial degradation step occurs with release of Cl, which then reacts with remaining part of the complex molecule in an exothermic process. This leads to decomposition of the ligand molecule into four fragments corresponding to ethyl chloride, carbon dioxide, methyl amine, and the fragment with the aromatic group. Mass spectrum suggests that creation of thes...e fragments most likely corresponds to the initial degradation, after which some of these coordinate to Pd center, whose coordination sphere is left incomplete by release of Cl. TG measurement to 1123 K indicates that the final degradation product at this temperature is palladium. (C) 2014 Elsevier B.V. All rights reserved.
Кључне речи:
Palladium complex / Thermal degradation / DFT calculations / Reaction mechanism / Chelate ligandИзвор:
Thermochimica Acta, 2014, 592, 23-30Издавач:
- Elsevier Science Bv, Amsterdam
Финансирање / пројекти:
- Динамика нелинеарних физичкохемијских и биохемијских система са моделирањем и предвиђањем њихових понашања под неравнотежним условима (RS-MESTD-Basic Research (BR or ON)-172015)
- Експериментална и теоријска проучавања реактивности и биолошка активност стереодефинисаних тиазолидина и синтетичких аналога (RS-MESTD-Basic Research (BR or ON)-172020)
- Интеракције природних производа, њихових деривата и комплексних једињења са протеинима и нуклеинским киселинама (RS-MESTD-Basic Research (BR or ON)-172055)
DOI: 10.1016/j.tca.2014.08.005
ISSN: 0040-6031
WoS: 000343020000004
Scopus: 2-s2.0-84906245359
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Begović, Nebojša AU - Blagojević, Vladimir A. AU - Ostojić, Sanja B. AU - Micić, Darko M. AU - Filipović, Nenad R. AU - Anđelković, Katarina K. AU - Minić, Dragica M. PY - 2014 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1862 AB - Thermal stability of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands was investigated using a combination of experimental measurements and DFT calculations. All complexes exhibit a reversible second-order transition around 333 K, which can be attributed to structural reorganization of the ligand molecules. Thermal degradation begins in 570-610 K temperature region, with an endothermic peak, followed by exothermic peaks in DSC. TG measurements show a well-defined mass loss corresponding to the initial degradation, while subsequent processes are poorly separated. DFT calculations suggest that the initial degradation step occurs with release of Cl, which then reacts with remaining part of the complex molecule in an exothermic process. This leads to decomposition of the ligand molecule into four fragments corresponding to ethyl chloride, carbon dioxide, methyl amine, and the fragment with the aromatic group. Mass spectrum suggests that creation of these fragments most likely corresponds to the initial degradation, after which some of these coordinate to Pd center, whose coordination sphere is left incomplete by release of Cl. TG measurement to 1123 K indicates that the final degradation product at this temperature is palladium. (C) 2014 Elsevier B.V. All rights reserved. PB - Elsevier Science Bv, Amsterdam T2 - Thermochimica Acta T1 - Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands VL - 592 SP - 23 EP - 30 DO - 10.1016/j.tca.2014.08.005 ER -
@article{ author = "Begović, Nebojša and Blagojević, Vladimir A. and Ostojić, Sanja B. and Micić, Darko M. and Filipović, Nenad R. and Anđelković, Katarina K. and Minić, Dragica M.", year = "2014", abstract = "Thermal stability of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands was investigated using a combination of experimental measurements and DFT calculations. All complexes exhibit a reversible second-order transition around 333 K, which can be attributed to structural reorganization of the ligand molecules. Thermal degradation begins in 570-610 K temperature region, with an endothermic peak, followed by exothermic peaks in DSC. TG measurements show a well-defined mass loss corresponding to the initial degradation, while subsequent processes are poorly separated. DFT calculations suggest that the initial degradation step occurs with release of Cl, which then reacts with remaining part of the complex molecule in an exothermic process. This leads to decomposition of the ligand molecule into four fragments corresponding to ethyl chloride, carbon dioxide, methyl amine, and the fragment with the aromatic group. Mass spectrum suggests that creation of these fragments most likely corresponds to the initial degradation, after which some of these coordinate to Pd center, whose coordination sphere is left incomplete by release of Cl. TG measurement to 1123 K indicates that the final degradation product at this temperature is palladium. (C) 2014 Elsevier B.V. All rights reserved.", publisher = "Elsevier Science Bv, Amsterdam", journal = "Thermochimica Acta", title = "Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands", volume = "592", pages = "23-30", doi = "10.1016/j.tca.2014.08.005" }
Begović, N., Blagojević, V. A., Ostojić, S. B., Micić, D. M., Filipović, N. R., Anđelković, K. K.,& Minić, D. M.. (2014). Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands. in Thermochimica Acta Elsevier Science Bv, Amsterdam., 592, 23-30. https://doi.org/10.1016/j.tca.2014.08.005
Begović N, Blagojević VA, Ostojić SB, Micić DM, Filipović NR, Anđelković KK, Minić DM. Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands. in Thermochimica Acta. 2014;592:23-30. doi:10.1016/j.tca.2014.08.005 .
Begović, Nebojša, Blagojević, Vladimir A., Ostojić, Sanja B., Micić, Darko M., Filipović, Nenad R., Anđelković, Katarina K., Minić, Dragica M., "Thermally induced structural transformations of a series of palladium(II) complexes with N-heteroaromatic bidentate hydrazone ligands" in Thermochimica Acta, 592 (2014):23-30, https://doi.org/10.1016/j.tca.2014.08.005 . .