Synthesis,Structural Characterization And Properties Of Organotin Complexes Derived From Phosphonic Acid

Organotin complexes have received widespread attention due to their diverse structures and their application in synthesis,catalysis,sterilization and antisepsis,especially in vitro cytostatic activity.Recently,the structure and properties of organotin??? compounds based on carboxylic acid have been extensively studied.Compared with organotin??? carboxylates,there have been relatively lesser reports on the organotin??? phosphonate complexes.Thus,exploring the structural characteristics and structure-activity relationship with biological activity of organotin ??? phosphonate complexes would become a promising research topic.The phosphoric acid groups contain three oxygen atoms and have potential coordination ability as well as variable coordination modes,which play an important role in the construction of organotin??? phosphonate complexes.In order to investigate the structure,properties and structure-activity relationship of organotin phosphonate compounds,we designed and synthesised a series of phosphonic acid ligands and obtained fifteen novel organotin phosphonate complexes.In this paper,we discussed the structures and studied the properties of organotin phosphonate complexes.The main works of this paper are displayed as below.1.Four homochiral organotin phosphonate complexes 1-4 and racemic organotin complex 5 were synthesized by the reactions of di or triorganotin substrates with?R?or?S?-?1-phenylethylamine?methylphosphonic acid?pempH₂?and racemic ligand,respectively.The X-ray crystallography determinations indicate that complexes 1-4 display 1D left-handed helical chain?1?,right-handed helical chain?2?and 1D infinite zig-zag chain structure,respectively?3 and 4?.Meanwhile,the complex 5 exhibits an axisymmetric cage structure.Furethmore,the in vitro anti-tumour activity of the organotin phosphonate complexes 1-4 against two tumour human cell lines,HeLa?the human cervix tumor cells?and HepG-2?the human hepatocellular carcinoma cells?,have been evaluated preliminarily by means of the MTT assays.The results presented that the complexes with R=phenyl?3and 4?show the higher activity than the R=methyl?1 and 2?against two tumour human cell lines,and the cytostatic activity for complexes 1-4 against HeLa cell are higher than against HepG-2.2.We took D-phenylglycine as raw materials to synthesize a racemic2-phenyl-2-?phosphonomethyl amino?acetic acid?ppaH3?ligand,and investigated the reactions of di or triorganotin substrates with the ppaH3 ligand.Four novel racemic organotin phosphonate complexes 6-9 were obtained and characterized by X-ray diffraction.The results indicate that the organotin??? phosphonate complexes 6-9 display1D infinite network polymers structure?6?,1D infinite ribbonlike polymer structure?7?,racemic dimer?8?and monomeric structure containing a dichloromethane solvent molecules?9?,respectively.Furthermore,the biological activity research of complexes 6-9against HeLa and HepG-2 cells,were carried out with MTT-based assays.Complexes 6-9have better biological activity against Hela and HepG-2 cells,among which complexes 8?R=Ph₂?and 9?R=Bu₂?display the higher activity for the cell growth-suppression than complexes 6?R=Me₃?and 7?R=Me₂?.3.Six organotin phosphonate complexes 10-15 were synthesized by the reactions of triorganotin chlorides?Me₃SnCl,Ph₃SnCl?with 1-naphthyl phosphate monosodium salt monoydrate ?NaHL¹?,naphthalen-1-ylphosphonic acid?H₂L²? and naphthalen-2-ylphosphonic acid?H₂L³?,respectively.The results indicate that the organotin complexes based on 1-naphthyl phosphate monosodium salt monohydrate display 1D chain structure?10?and 24-membered macrocyclic rings?13?,respectively.The organotin complexes based on naphthalen-1-ylphosphonic acid exhibit 1D right-handed helical chain structure?11?and 1D infinite zig-zag chain structure?14?,respectively.Meanwhile,the organotin naphthalen-2-ylphosphonates show 1D left-handed helical chain structure?12?and 24-membered macrocyclic rings?15?,respectively.Complexes 10-12 are chiral organotin phosphonate complexes which are obtained by spontaneous crystallization of achiral ligands,which has become a potential research hotspot in the field of building chiral materials.At the same time,preliminarily in vitro cytostatic activity studies on HeLa and HepG-2 by MTT assay for complexes 10-15 have been investigated.The outcomes reveal that complexes with R=phenyl?13-15?show the higher cytostatic activity than the R=methyl?10-12?against HeLa and HepG-2,and the cytostatic activity for complexes10-15 against HeLa cell are higher than against HepG-2.