doktorska disertacija
Povzetek
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
Ključne besede
cink(II);baker(II);kinaldinat;ciklični amini;amidini;amino alkoholi;kristalne strukture;teoretični izračuni;magnetne lastnosti;doktorske disertacije;
Podatki
Jezik: |
Slovenski jezik |
Leto izida: |
2022 |
Tipologija: |
2.08 - Doktorska disertacija |
Organizacija: |
UL FKKT - Fakulteta za kemijo in kemijsko tehnologijo |
Založnik: |
[N. Podjed] |
UDK: |
546.47:547.594.5(043.3) |
COBISS: |
126043139
|
Št. ogledov: |
91 |
Št. prenosov: |
15 |
Ocena: |
0 (0 glasov) |
Metapodatki: |
|
Ostali podatki
Sekundarni jezik: |
Angleški jezik |
Sekundarni naslov: |
Study of zinc(ll) and copper(ll) quinaldinate reactions with cyclic amines and amino alcohols |
Sekundarni povzetek: |
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. |
Sekundarne ključne besede: |
coordination chemistry;zinc(II);copper(II);quinaldinate;cyclic amines;amidines;amino alcohols;crystal structure;theoretical calculations;magnetic properties;Koordinacijske spojine;Univerzitetna in visokošolska dela; |
Vrsta dela (COBISS): |
Doktorsko delo/naloga |
Študijski program: |
1000381 |
Konec prepovedi (OpenAIRE): |
1970-01-01 |
Komentar na gradivo: |
Univ. v Ljubljani, Fak. za kemijo in kemijsko tehnologijo |
Strani: |
XXVII, 270 str., P1-P23 |
ID: |
16619321 |