Kompleksi platine(II) i rutenijuma(II) sa diaminskim ligandima: sinteza, karakterizacija i citotoksičnost

Abstract

U ovom radu su opisani sinteza, karakterizacija i biološka aktivnost nove (S,S)- 1,3-propandiamin-N,N’-di-2-(3-cikloheksil)propanske kiseline i njenih estara (metil, etil, n-propil, n-butil, izobutil, n-pentil i izopentil), koji su korišćeni za sintezu kvadratno-planarnih Pt(II) jodido kompleksa, opšte formule [PtI2{(S,S)-R2pddchxp}]. Takođe je opisana sinteza, karakterizacija i biološka aktivnost novih organorutenijum(II) kompleksa sa estrima (S,S)-etandiamin-N,N’-di-2-(3- cikloheksil)propanske kiseline (metil, etil, n-propil, n-butil, izobutil i izopentil), opšte formule [(η6-p-cimen)RuCl{(S,S)-R2eddchxp}]PF6. Polazna kiselina je dobijena u reakciji (S)-2-amino-3-cikloheksilpropanske kiseline i 1,3-dibrompropana u vodenom rastvoru, dok je njena esterifikacija izvršena pomoću tionil-hlorida i odgovarajućeg alkohola. Jodido kompleksi platine(II) su dobijeni reakcijom kalijum-tetrahloridoplatinata(II) i odgovarajućih estara, uz dodatak kalijum-jodida, dok su odgovarajući rutenijum(II) kompleksi sintetisani u reakciji između [(η6-p-cimen)RuCl2]2 i estara (S,S)-etandiamin-N,N’-di-2-(3- cikloheksil)propanske kiseline. Karakterizacija liganada je urađena klasičnim metodama: elementalnom analizom, IC, (1H i 13C) NMR spektroskopijom i masenom spektrometrijom, dok su kompleksi pored navedenih metoda, okarakterisani i elektronskom apsorpcionom spektroskopijom, rendgenskom strukturnom analizom za kompleks [(η6-pcimen) RuCl{(S,S)-iBu2eddchxp}]PF6 i 195Pt NMR spektroskopijom za kompleks [PtI2{(S,S)-iBu2pddchxp}]. Na osnovu rezultata dobijenih karakterizacijom, utvrđeno je da kompleksi platine(II) imaju kvadratno-planarnu strukturu, sa N,N’ bidentatno vezanim estarskim ligandima. Na osnovu rendgenske-strukturne analize kompleksa [(η6-p-cimen)RuCl{(S,S)-iBu2eddchxp}]PF6, potvrđena je pseudo-oktaedarska geometrija sintetisanih Ru(II) kompleksa, sa koordinacijom estarskog liganda preko...

In this work, the synthesis, characterization and biological activity of novel (S,S)-1,3-propanediamine-N,N’-di-2-(3-cyclohexyl)propanoic acid, its esters (methyl, ethyl, n-propyl, n-butyl, i-butyl, n-pentyl and i-pentyl) and corresponding square-planar iodido Pt(II) complexes, of general formula [PtI2{(S,S)-R2pddchxp}], are presented. In addition, the synthesis, characterization and biological activity of novel organorutenium(II) complexes with esters of (S,S)-ethanediamine-N,N’-di-2-(3- cyclohexyl)propanoic acid (methyl, ethyl, n-propyl, n-butyl, i-butyl and i-pentyl), general formula, of [(η6-p-cimen)RuCl{(S,S)-R2eddchxp}]PF6, were reported. Starting acid was obtained by reaction of (S)-2-amino-3-cyclohexyl-propanoic acid and 1,3-dibromopropane, in water solution, while esterification was performed with thionyl chloride and corresponding alcohol. Iodido complexes of platinum(II) were obtained by reaction of potassium tetrachloridoplatinate(II) and synthesized esters, with adding of potassium iodide. Ruthenium(II) complexes were synthesized by reaction between [(η6-p-cymene)RuCl2]2 and different esters of (S,S)-ethanediamine-N,N’-di-2- (3-cyclohexyl)propanoic acid. Ligands were characterized by elemental analysis, IR, (1H and 13C) NMR spectroscopy and mass spectrometry, while the complexes, in addition to these methods, were characterized and UV/Vis, single crystal X-ray structure diffraction analysis for [(η6-p-cymene)RuCl{(S,S)-iBu2eddchxp}]PF6 and 195Pt NMR spectroscopy for [PtI2{(S,S)-iBu2pddchxp}]. Based on these results, it is found that complexes platinum(II) have square-planar geometry with coordination of ligands via nitrogen donor atoms of ester ligands. Single crystal X-ray structure diffraction analysis of [(η6-p-cymene)RuCl{(S,S)-iBu2eddchxp}]PF6 showed the usual piano-stool geometry of complexes, with N,N’ coordination of ester ligands. The stability of the complexes of platinum and ruthenium in different solvents was investigated, as well as the ability of these complexes to bind lysozyme...