Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes
Аутори
Adejumo, Temiloluwa T.TZOURAS, NIKOLAOS
Zorba, Leandros
Radanović, Dušanka D.
Pevec, Andrej
Grubišić, Sonja
Mitić, Dragana
Anđelković, Katarina K.
Vougioukalakis, Georgios
Čobeljić, Božidar
Turel, Iztok
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivit...y descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.
Кључне речи:
Girard’s T reagent / hydrazone ligand / Zn(II) complexes / XRD / ketone-amine-alkyne coupling reaction / catalysis / DFT calculationИзвор:
Molecules, 2020, 25, 18, 4043-Издавач:
- MDPI
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200168 (Универзитет у Београду, Хемијски факултет) (RS-MESTD-inst-2020-200168)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200026 (Универзитет у Београду, Институт за хемију, технологију и металургију - ИХТМ) (RS-MESTD-inst-2020-200026)
DOI: 10.3390/molecules25184043
ISSN: 1420-3049
WoS: 000579956700001
Scopus: 2-s2.0-85090753294
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Adejumo, Temiloluwa T. AU - TZOURAS, NIKOLAOS AU - Zorba, Leandros AU - Radanović, Dušanka D. AU - Pevec, Andrej AU - Grubišić, Sonja AU - Mitić, Dragana AU - Anđelković, Katarina K. AU - Vougioukalakis, Georgios AU - Čobeljić, Božidar AU - Turel, Iztok PY - 2020 UR - http://cherry.chem.bg.ac.rs/handle/123456789/5691 AB - Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivity descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule. PB - MDPI T2 - Molecules T1 - Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes VL - 25 IS - 18 SP - 4043 DO - 10.3390/molecules25184043 ER -
@article{ author = "Adejumo, Temiloluwa T. and TZOURAS, NIKOLAOS and Zorba, Leandros and Radanović, Dušanka D. and Pevec, Andrej and Grubišić, Sonja and Mitić, Dragana and Anđelković, Katarina K. and Vougioukalakis, Georgios and Čobeljić, Božidar and Turel, Iztok", year = "2020", abstract = "Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivity descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.", publisher = "MDPI", journal = "Molecules", title = "Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes", volume = "25", number = "18", pages = "4043", doi = "10.3390/molecules25184043" }
Adejumo, T. T., TZOURAS, N., Zorba, L., Radanović, D. D., Pevec, A., Grubišić, S., Mitić, D., Anđelković, K. K., Vougioukalakis, G., Čobeljić, B.,& Turel, I.. (2020). Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes. in Molecules MDPI., 25(18), 4043. https://doi.org/10.3390/molecules25184043
Adejumo TT, TZOURAS N, Zorba L, Radanović DD, Pevec A, Grubišić S, Mitić D, Anđelković KK, Vougioukalakis G, Čobeljić B, Turel I. Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes. in Molecules. 2020;25(18):4043. doi:10.3390/molecules25184043 .
Adejumo, Temiloluwa T., TZOURAS, NIKOLAOS, Zorba, Leandros, Radanović, Dušanka D., Pevec, Andrej, Grubišić, Sonja, Mitić, Dragana, Anđelković, Katarina K., Vougioukalakis, Georgios, Čobeljić, Božidar, Turel, Iztok, "Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes" in Molecules, 25, no. 18 (2020):4043, https://doi.org/10.3390/molecules25184043 . .