@conference{
author = "Jevtović, Mima and Savić, Milica and Anđelković, Katarina and Čobeljić, Božidar and Mitić, Dragana",
year = "2023",
abstract = "The ligand (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide (HL1 ) was obtained from the condensation of 2-acetylthiazole and thiosemicarbazide. Upon reacting HL1 with Zn(BF4)2·6H2O and NaN3 in a solvent mixture of water/methanol, mononuclear Zn(II) complex 1 with the composition [ZnL1 (N3)2] was obtained. In complex 1, Zn(II) is pentacoordinated with the thiazole nitrogen, the azomethine nitrogen, and thiolate sulfur atoms from the deprotonated hydrazone ligand, as well as with two azido ligands. Complex 1 crystallises in the monoclinic crystal system with space group No.14 (P21/c cell setting). The unit cell of 1 contains four [ZnL1 (N3)] asymmetric units. In complex 1, the Zn(II) site shows a distorted geometry, almost midway between the square pyramid and trigonal bipyramid, established on the basis of a calculated τ5 parameter of 0.46. The hydrazone ligand (E)-1-(2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethyl)-pyridine1-ium chloride (HL2 Cl) was obtained from the condensation reaction of 2-acetylpyridine and Girard's P reagent. Reaction of HL2 Cl with Zn(BF4)2·6H2O and NaN3, in a mixture of acetonitrile/water/methanol, gives mononuclear Zn(II) complex 2 with the composition [ZnL2 (N3)2]. Reaction of HL2 Cl with Zn(BF4)2·6H2O and NaN3, in a mixture of acetonitrile/water/methanol, gives mononuclear Zn(II) complex 2 with the composition [ZnL2 (N3)2]. In complex 2, the Zn(II) ion has fivefold coordination with NNO-set of donor atoms of L2 and two nitrogen atoms from the azido ligands. The calculated τ5 value of 0.08 for [ZnL2 (N3)2] indicates that the five-coordination geometry of the Zn(II) ion is slightly distorted square pyramidal. Evaluation of the catalytic properties of the Zn(II) complexes in the KA2 reaction shows that the most active compound, when used as a catalyst, is complex 1. It leads to a 92 % isolated yield of the desired propargylamine product. The catalytic activity results are in full agreement with the findings of the DFT calculations. Complex 1 shows the highest value of molecular softness and the lowest value of molecular hardness. This correlation, between experimental and theoretical results, is excellently visualised in the linear relationship between the isolated yield of the desired propargylamine product and the calculated molecular softness, S.",
publisher = "COST action CA21101 (COSY)",
journal = "Book of abstracts - COST Training School, COST action CA21101 COSY, "Multiscale modeling of the properties of compounds: From isolated molecules to 3D materials relevant for industrial and astrophysical applications," 19th - 22nd September, 2023, Belgrade",
title = "Synthesis of a New Family of Zn(II) Hydrazone Complexes: Characterisation, Catalytic Activity, and DFT Calculations",
pages = "36-36",
url = "https://hdl.handle.net/21.15107/rcub_cer_7319"
}