Preučevanje reakcij cinkovega(ll) in bakrovega(ll) kinaldinata s cikličnimi amini ter amino alkoholi

Podjed, Nina (avtor), Modec, Barbara (mentor)

Cink in baker sta esencialna elementa v sledovih, ki sta izjemno pomembna za vsa živa bitja. Veliko zanimanje za njuno koordinacijsko kemijo izhaja prav iz potrebe po globljem razumevanju biološke vloge. Ob pregledu literature smo ugotovili, da kemija cinka(II) in bakra(II) s kinaldinatom (anion kinolin-2-karboksilne kisline) ni dobro raziskana. V okviru doktorske disertacije smo zato preučevali reakcije cinkovega(II) in bakrovega(II) kinaldinata s cikličnimi amini in amino alkoholi. Pri sistemih s cinkom(II) in amini smo v treh različnih nitrilih (acetonitrilu, propionitrilu in benzonitrilu) dokazali, da lahko cink(II) deluje podobno kot v encimih in katalizira reakcijo med cikličnim aminom in nitrilom, pri čemer nastane amidin. Pripravili smo raznolike produkte: nevtralne komplekse s kinaldinatom in koordiniranimi amini ali amidini ter ionske spojine. Slednje so bile sestavljene iz protoniranega amina ali amidina in anionskega homoleptičnega kompleksa s tremi kinaldinati. Analogne reakcije z bakrovim(II) kinaldinatom so vodile do izolacije kompleksov s koordinirani amini. Pri bakru(II) je v nekaterih primerih prišlo do oksidacijsko-redukcijskih reakcij. Pri piperidinu smo redukcijo dejansko dokazali s pridobitvijo kristalne strukture policiklične piperidinske spojine. Reakcije z amino alkoholi so vodile do strukturno zelo raznolikih bakrovih(II) spojin, saj smo sintetizirali enojedrne, dvojedrne in tudi enodimenzionalne polimerne zvrsti z amino alkoholi ali amino alkoholati. Cinkovi(II) sistemi z amino alkoholi so pokazali, da lahko slednji pri ostrih pogojih razpadejo do amonijaka. Bogata strukturna raznolikost produktov je potrdila veliko koordinacijsko fleksibilnost obeh kovinskih ionov. Ugotovili smo, da lahko isti ligandi drugače reagirajo v prisotnosti cinka(II) in bakra(II), pri čemer pomembno vlogo igrajo tudi reakcijski pogoji. Sintetiziranih je bilo več kot sto spojin z dušik- in kisik-donorskimi ligandi, ki smo jih okarakterizirali z različnimi fizikalno-kemijskimi metodami: infrardečo spektroskopijo, jedrsko magnetno resonančno spektroskopijo, elementno analizo, masno spektrometrijo visoke ločljivosti in rentgensko strukturno analizo na monokristalu. V sodelovanju z raziskovalno skupino dr. Joaquína López-Serrana (Univerza v Sevilli) so bili za nekatere spojine izvedeni teoretični DFT izračuni predvsem za primerjavo relativnih stabilnosti. V sodelovanju z raziskovalno skupino dr. Rodolpha Cléraca (Univerza v Bordeauxu) so bile izmerjene in analizirane magnetne lastnosti bakrovih(II) spojin s kinaldinatom in amino alkoholnimi ligandi

• Jezik: Slovenski jezik
• Ključne besede: koordinacijska kemija, cink(II), baker(II), kinaldinat, ciklični amini, amidini, amino alkoholi, kristalne strukture, teoretični izračuni, magnetne lastnosti
• Vrsta gradiva: Doktorsko delo/naloga
• Tipologija: 2.08 - Doktorska disertacija
• Organizacija: FKKT - Fakulteta za kemijo in kemijsko tehnologijo
• Leto izida: 2022
• PID: 20.500.12556/RUL-141522
• COBISS.SI-ID: 126043139
• Datum objave v RUL: 30.09.2022

PODJED, Nina, 2022, Preučevanje reakcij cinkovega(ll) in bakrovega(ll) kinaldinata s cikličnimi amini ter amino alkoholi [na spletu]. Doktorska disertacija. [Dostopano 10 april 2025]. Pridobljeno s: https://repozitorij.uni-lj.si/IzpisGradiva.php?lang=slv&id=141522

Sekundarni jezik

• Jezik: Angleški jezik
• Naslov: Study of zinc(ll) and copper(ll) quinaldinate reactions with cyclic amines and amino alcohols

Izvleček

Zinc and copper are essential trace elements that are extremely important for all living things. The fundamental motive for vast interest in their coordination chemistry stems from the need for a deeper understanding of their biological role. A review of the literature revealed that the chemistry of zinc(II) and copper(II) with quinaldinate (anion of quinoline-2-carboxylic acid) is not well understood. Therefore, the reactions of zinc(II) and copper(II) quinaldinate with cyclic amines and amino alcohols were investigated. Systems with zinc(II) and amines in three different nitriles (acetonitrile, propionitrile and benzonitrile) showed that zinc(II) can catalyze the reaction between a cyclic amine and a nitrile, yielding an amidine. A variety of products have been prepared: neutral complexes with quinaldinate and coordinated amines or amidines and ionic compounds. The latter consisted of a protonated amine or amidine and an anionic homoleptic complex with three quinaldinates. Analogous reactions with copper(II) quinaldinate led to the isolation of complexes with coordinated amines. In the case of copper(II), oxidation-reduction reactions occurred in some cases. In the case of piperidine, the reduction was indeed proved by the crystal structure of a polycyclic piperidine compound. Reactions with amino alcohols led to structurally very diverse copper(II) compounds: mononuclear, binuclear and also one-dimensional polymeric species with amino alcohols or amino alcoholates. Zinc(II) systems with amino alcohols have shown that the amino alcohols can decompose to ammonia under forcing conditions. The rich structural diversity of the products confirmed the high coordination flexibility of the two metal ions. The same ligands can react differently in the presence of zinc(II) or copper(II), with the reaction conditions also playing an important role. More than a hundred compounds with nitrogen- and oxygen-donor ligands were synthesized and characterized by different physicochemical methods: infrared spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, high-resolution mass spectrometry and single crystal X-ray structural analysis. In collaboration with the research group of Dr. Joaquín López-Serrano (University of Seville), theoretical DFT calculations were performed for some compounds, mainly to compare their relative stabilities. In collaboration with the research group of Dr. Rodolphe Clérac (University of Bordeaux), the magnetic properties of copper(II) compounds with quinaldinate and amino alcohol ligands were measured and analyzed.

• Ključne besede: coordination chemistry, zinc(II), copper(II), quinaldinate, cyclic amines, amidines, amino alcohols, crystal structures, theoretical calculations, magnetic properties