Stereochemistry of 2,2'-iminodiacetamide and bis(2-pyridine-2-ylmethyl)amine complexes and their application in enantioselective catalysis

Abstract

U okviru ove disertacije proučavana je stereokemija kompleksa 2,2'-iminodiacetamida i bis(piridin-2-ilmetil)amina, te je ispitan utjecaj supstituenata na ligandu, aniona, i nekovalentnih interakcija. Pripravljeni ligandi podijeljeni su u četiri skupine. Priređeno je 8 različito supstituiranih iminodiacetamidnih liganada (A) te je istražen utjecaj supstituenata na stereokemiju metalnih kompleksa. S H-supstituiranim ligandom dobivena je kristalna struktura cis-fac kompleksa, dok su s ostalim ligandima dobiveni trans-fac izomeri. S izopropilsupstituiranim bis(piridin-2-ilmetil)aminskim ligandom (B) priređeni su kompleksi koristeći Cu(II) i Zn(II) s različitim anionima. Ovisno o anionu, dobivene su kristalne strukture monomera, dimera, cis-fac-ML2 kompleksa te ciklički trimer koji veže CO2 iz zraka. Kompleksi Fe(II) s 2 cikloheksandiaminska derivata (C) ispitani su u katalitičkim reakcijama kao mimici enzima flavon sintaze. Također je priređeno 7 bis(piridin-2-ilmetil)aminskih i 5 iminodiacetamidnih liganada (D) s različitom duljinom CH2 poveznice i različitim kiralnim skupinama kako bi se istražio utjecaj strukturnih promjena na koordinacijska svojstva liganada u kompleksima Cu(II) i Zn(II). Ligandi s 3 CH2 skupine tvorili su komplekse ML2 stehiometrije, dok je kod liganada s 2 CH2 skupine došlo do koordinacije pokrajnjeg lanca i stvaranja ML kompleksa. Kompleksi ML stehiometrije pokazali su aktivnost u DNA cijepanju.In this dissertation, the stereochemistry of 2,2'-iminodiacetamide and bis(pyridin-2-ylmethyl) amine ligand complexes was studied, focusing on the influence of substituents on the ligand, anion and noncovalent interactions. The prepared ligands were divided into four groups. Eight differently substituted iminodiacetamide ligands (A) were prepared. A cis-fac crystal structure was obtained with the H-substituted ligand, while the other ligands gave trans-fac isomers. Complexes with Cu(II) and Zn(II) were prepared with a isopropyl-substituted bis(2-pyridine- 2-ylmethyl)amine ligand (B). Depending on the anion, crystal structures of monomers, dimers, a cis-fac-ML2 complex and a cyclic trimer that binds CO2 from air were obtained. Fe(II) complexes with two cyclohexanediamine derivatives (C) were investigated in catalytic reactions as flavone synthase mimics. Furthermore, 7 bis(2-pyridine-2-ylmethyl)amine and 5 iminodiacetamide ligands (D) with different lengths of CH2 linkers and different chiral groups were prepared to study the influence of structural changes on the coordination properties of these ligands in Cu(II) and Zn(II) complexes. Ligands with 3 CH2 groups formed ML2 complexes, while ligands with 2 CH2 groups showed side chain coordination and formation of ML complexes. Complexes of ML stoichiometry showed DNA cleavage activity