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 <b>1</b>, <b&g...
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doaj-9bd5bd40568840b989af21710d83e5582020-11-25T03:26:58ZengMDPI AGMolecules1420-30492020-09-01254043404310.3390/molecules25184043Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone ComplexesTemiloluwa T. Adejumo0Nikolaos V. Tzouras1Leandros P. Zorba2Dušanka Radanović3Andrej Pevec4Sonja Grubišić5Dragana Mitić6Katarina K. Anđelković7Georgios C. Vougioukalakis8Božidar Čobeljić9Iztok Turel10Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11000 Belgrade, SerbiaLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 15771 Athens, GreeceLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 15771 Athens, GreeceCenter for Chemistry, ICTM, University of Belgrade, Njegoševa 12, P.O. Box 815, 11001 Belgrade, SerbiaFaculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000 Ljubljana, SloveniaCenter for Chemistry, ICTM, University of Belgrade, Njegoševa 12, P.O. Box 815, 11001 Belgrade, SerbiaInnovation Centre of Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11000 Belgrade, SerbiaFaculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11000 Belgrade, SerbiaLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 15771 Athens, GreeceFaculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11000 Belgrade, SerbiaFaculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000 Ljubljana, SloveniaTwo 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 <b>1</b>, <b>2</b> and recently synthesized [Zn<b>L<sup>3</sup></b>(NCS)<sub>2</sub>] (<b>L<sup>3</sup></b> = (<i>E</i>)-<i>N</i>,<i>N</i>,<i>N</i>-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex <b>3</b> were tested as potential catalysts for the ketone-amine-alkyne (KA<sup>2</sup>) 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 (<i>μ</i>), hardness (<i>η</i>), softness (<i>S</i>), electronegativity (<i>χ</i>) and electrophilicity index (<i>ω</i>) have been calculated. The energetic behavior of the investigated compounds (<b>1</b> and <b>2</b>) 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 [Zn<b>L<sup>3</sup></b>(NCS)<sub>2</sub>] complex <b>3</b>. DFT results show that compound <b>1</b> 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.https://www.mdpi.com/1420-3049/25/18/4043Girard’s T reagenthydrazone ligandZn(II) complexesXRDketone-amine-alkyne coupling reactioncatalysis |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Temiloluwa T. Adejumo Nikolaos V. Tzouras Leandros P. Zorba Dušanka Radanović Andrej Pevec Sonja Grubišić Dragana Mitić Katarina K. Anđelković Georgios C. Vougioukalakis Božidar Čobeljić Iztok Turel |
spellingShingle |
Temiloluwa T. Adejumo Nikolaos V. Tzouras Leandros P. Zorba Dušanka Radanović Andrej Pevec Sonja Grubišić Dragana Mitić Katarina K. Anđelković Georgios C. Vougioukalakis Božidar Čobeljić Iztok Turel Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes Molecules Girard’s T reagent hydrazone ligand Zn(II) complexes XRD ketone-amine-alkyne coupling reaction catalysis |
author_facet |
Temiloluwa T. Adejumo Nikolaos V. Tzouras Leandros P. Zorba Dušanka Radanović Andrej Pevec Sonja Grubišić Dragana Mitić Katarina K. Anđelković Georgios C. Vougioukalakis Božidar Čobeljić Iztok Turel |
author_sort |
Temiloluwa T. Adejumo |
title |
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_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_sort |
synthesis, characterization, catalytic activity, and dft calculations of zn(ii) hydrazone complexes |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2020-09-01 |
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 <b>1</b>, <b>2</b> and recently synthesized [Zn<b>L<sup>3</sup></b>(NCS)<sub>2</sub>] (<b>L<sup>3</sup></b> = (<i>E</i>)-<i>N</i>,<i>N</i>,<i>N</i>-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex <b>3</b> were tested as potential catalysts for the ketone-amine-alkyne (KA<sup>2</sup>) 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 (<i>μ</i>), hardness (<i>η</i>), softness (<i>S</i>), electronegativity (<i>χ</i>) and electrophilicity index (<i>ω</i>) have been calculated. The energetic behavior of the investigated compounds (<b>1</b> and <b>2</b>) 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 [Zn<b>L<sup>3</sup></b>(NCS)<sub>2</sub>] complex <b>3</b>. DFT results show that compound <b>1</b> 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. |
topic |
Girard’s T reagent hydrazone ligand Zn(II) complexes XRD ketone-amine-alkyne coupling reaction catalysis |
url |
https://www.mdpi.com/1420-3049/25/18/4043 |
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