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Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes
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...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7570652/ https://www.ncbi.nlm.nih.gov/pubmed/32899683 http://dx.doi.org/10.3390/molecules25184043 |
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author | Adejumo, Temiloluwa T. Tzouras, Nikolaos V. Zorba, Leandros P. Radanović, Dušanka Pevec, Andrej Grubišić, Sonja Mitić, Dragana Anđelković, Katarina K. Vougioukalakis, Georgios C. Čobeljić, Božidar Turel, Iztok |
author_facet | Adejumo, Temiloluwa T. Tzouras, Nikolaos V. Zorba, Leandros P. Radanović, Dušanka Pevec, Andrej Grubišić, Sonja Mitić, Dragana Anđelković, Katarina K. Vougioukalakis, Georgios C. Čobeljić, Božidar Turel, Iztok |
author_sort | Adejumo, Temiloluwa T. |
collection | PubMed |
description | 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 [ZnL(3)(NCS)(2)] (L(3) = (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 (KA(2)) 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 [ZnL(3)(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. |
format | Online Article Text |
id | pubmed-7570652 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-75706522020-10-28 Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes Adejumo, Temiloluwa T. Tzouras, Nikolaos V. Zorba, Leandros P. Radanović, Dušanka Pevec, Andrej Grubišić, Sonja Mitić, Dragana Anđelković, Katarina K. Vougioukalakis, Georgios C. Čobeljić, Božidar Turel, Iztok Molecules Article 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 [ZnL(3)(NCS)(2)] (L(3) = (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 (KA(2)) 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 [ZnL(3)(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. MDPI 2020-09-04 /pmc/articles/PMC7570652/ /pubmed/32899683 http://dx.doi.org/10.3390/molecules25184043 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Adejumo, Temiloluwa T. Tzouras, Nikolaos V. Zorba, Leandros P. Radanović, Dušanka Pevec, Andrej Grubišić, Sonja Mitić, Dragana Anđelković, Katarina K. Vougioukalakis, Georgios C. Čobeljić, Božidar Turel, Iztok Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title | Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title_full | Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title_fullStr | Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title_full_unstemmed | Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title_short | Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes |
title_sort | synthesis, characterization, catalytic activity, and dft calculations of zn(ii) hydrazone complexes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7570652/ https://www.ncbi.nlm.nih.gov/pubmed/32899683 http://dx.doi.org/10.3390/molecules25184043 |
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