@phdthesis{
author = "Adejumo, Temiloluwa T.",
year = "2024",
abstract = "In this study, a series of novel zinc complexes have been synthesised and thoroughly characterized. Two of the complexes were prepared from the ligands obtained from derivatives of 2-acetylthiazole, and another two from the derivative of Girard's reagents T and P. These complexes featured tridentate coordinating ligands of hydrazone with NNS or NNO donating atoms and were characterized by elemental analysis, spectroscopic techniques and single crystal XRD methods. In addition to these new complexes, the study also included a catalytic study of five analogues previously synthesized, each containing ligands with the same donor atom sets. The primary aim of this research was to evaluate the catalytic potential of these complexes in the
coupling reaction of KA2, leading to the synthesis of tetrasubstituted propargylamines, which are
commonly used as intermediates in organic synthesis, providing easy access to a wide range of
structurally complex organic compounds. A number of model reactants were used to optimise the
KA2 reaction conditions. To further investigate the catalytic activity of the Zn(II) complex, additional
tests were then carried out on the most reactive compounds using a variety of substrate combinations. In order to better understand the electronic structure of the complexes and how it correlates with catalytic reactivity, the study employed density functional theory (DFT) calculations. Based on the Conceptual DFT framework the study derived several global molecular reactivity descriptors, including chemical potential (µ), hardness (η), softness (S), electronegativity (χ), and electrophilic index (ω). These descriptors provided valuable insights into how reactive and stable complexes are., U ovoj tezi, sintetisana je i detaljno okarakterisana serija novih kompleksa Zn(II). Dva kompleksa su dobijena polazeći od liganda derivata 2-acetiltiazola, a druga dva od derivata Žirarovih T i P
reagenasa. Ovi kompleksi sadrže ligande na bazi tridentatnih hidrazona, sa NNO ili NNS donorskim setom atoma, i okarakterisani su elementalnom analizom, infracrvenom (IC) i nuklearno magnetno rezonantnom (NMR) spektroskopijom i metodom difrakcije rendgenskih zraka na monokristalima. Pored novih kompleksa Zn(II), studija je takođe uključila i pet prethodno sintetisanih analoga, koji sadrže ligande sa istim donorskim setom atoma. Glavni cilj ovog istraživanja bio je evaluacija katalitičkog potencijala kompleksa Zn(II), u reakciji keto-amin-alkin (KA2) kuplovanja, koja kao proizvod daje tetrasupstituisane propargilamine. Propargilamini se najčešće koriste kao intermedijeri u organskim sintezama, omogućavajući lak pristup širokom spektru kompleksnih organskih jedinjenja. Prilikom optimizacije KA2 reakcije korišćeni su različiti model sistemi. Kako bi se dodatna ispitala katalitička aktivnost kompleksa Zn(II), za nejreaktivnija jedinjenja, se potom pratio uticaj promenom polaznih supstrata na reaktivnost. DFT proračuni su izvedeni da bi se razjasnila elektronska struktura ispitivanih kompleksa Zn(II), odlično povezujući strukturu kompleksa sa njihovom katalitičkom aktivnošću. Na osnovu Konceptualne teorije funkcionala gustine, izračunati su globalni molekulski deskriptori reaktivnosti, kao što su hemijski potencijal (µ), tvrdoća (η), mekoća (S), elektronegativnost (χ) i indeks elektrofilnosti (ω). Ovi deskriptori su pružili uvid u to koliko su proučavani kompleksi reaktivni i stabilni.",
publisher = "Универзитет у Београду, Хемијски факултет",
journal = "Универзитет у Београду",
title = "Synthesis, characterization and evaluation of catalytic properties of Zn(II) complexes, Синтеза, карактеризација и испитивање каталитичких својстава комплекса Zn(II)"
}
