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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. 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. |
