Utjecaj središnjeg donorskog atoma na stereokemiju metalnih kompleksa s bis(piridin-2-ilmetil)aminskim i 2,2'-iminodiacetamidnim ligandima

master's thesis

• Title (english): Influence of the central donor atom on the stereochemistry of metal complex with bis(2-pyridine-2-ylmethyl)amine and 2,2'-iminodiacetamide ligands
• Author: Aleks Logožar
• Mentor: Srećko Kirin (mentor)
• Committee member: Đani Škalamera (predsjednik povjerenstva)
• Committee member: Biserka Prugovečki (član povjerenstva)
• Committee member: Ivan Nemet (član povjerenstva)
• Committee member: Željka Car (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2023-02-23, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog diplomskog rada proučavana je stereokemija ML2 kompleksa analoga
bis(piridin-2-ilmetil)amina i 2,2'-iminodiacetamida. Ispitan je utjecaj središnjeg donorskog
atoma na stabilnost izomera putem eksperimentalnog i računskog pristupa. U računalnom dijelu
modelirani su sustavi dvanaest odabranih liganada i četiriju dvovalentnih metalnih iona [Zn(II),
Cu(II), Ni(II) i Co(II)]. Dobiveno je ukupno 111 mogućih konformacija liganada, te 153 ML i
293 ML2 struktura kompleksa. Određena je relativna stabilnost izomera kao i pripadajuće
energije kompleksiranja za sve primjere. Sintetizirano je šest liganada, po 3 od svakog
ligandnog sustava. Kristalizacijskim eksperimentima dobiveno je ukupno dvanaest kristalnih
struktura; dva liganda, mer-ML kompleks, cis-fac-ML2, dva mer-ML2 i četiri trans-fac-ML2
kompleksa, kao i dva kokristala liganda sa solvatiranim metalnim ionima. U strukturama
kokristala uočen je zanimljiv motiv vodikovih veza. Rezultati istraživanja su uspoređeni i
iznesene su preference središnjih donorskih atoma ka određenim ML2 izomerima. Pokazano je
da kod sumpora i fosfora kao središnjih donorskih atoma mer-ML2 izomeri nisu stabilni.

Abstract (english)

In this master thesis, the stereochemistry of ML2 metal complexes of bis(2-pyridine-2-
ylmethyl)amine and 2,2'-iminodiacetamide analogues was examined. The influence of the
central donor atom on the stability of ML2 isomers was studied using both computational and
experimental techniques. In the computational modelling, combinations of twelve chosen
ligands and four divalent metal ions [Zn(II), Cu(II), Ni(II) and Co(II)] were examined. In total,
structures of 111 ligand conformers and 153 ML and 293 ML2 metal complexes were
calculated. Relative stability of isomers and the corresponding complexation energies were
determined. In the experimental part, six ligands were prepared, three from each of the chosen
ligand families. Crystallization experiments afforded crystal structures of twelve compounds:
two ligands, one mer-ML complex, one cis-fac-ML2, two mer-ML2 and four trans-fac-ML2
complexes, as well as two cocrystals of ligands and solvated metal ions. In the crystal structures
of the two cocrystals, an interesting motif of hydrogen bonding was observed. The results were
compared and preferences of the central donor atoms towards specific ML2 isomers were
revealed. It was also shown that mer-ML2 isomers of phosphorus and sulfur containing ligands
are not stable.

• Keywords: izomeri; metalni kompleksi; stereokemija; tridentatni ligandi
• Keywords (english): isomers; metal complexes; stereochemistry; tridentate ligands
• Language: croatian
• URN:NBN: urn:nbn:hr:217:380234
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2025-02-23
• Created on: 2023-03-30 13:03:50