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

As an important branch of organometallic chemistry,organotin?IV?compounds have attracted more and more attention from all walks of life for diversity of its bonding and universality of application.For the past few years,great advances had been achieved in the aspect of synthesis of organotin?IV?compounds based on carboxylic acid,schiff's base,sulfonic acid and so on.And in its biological activity research and selection process,we found that some organotin compounds possess higher antitumor activity than cisplatin.Hence,the synthesis of organotin compounds with novel structure and high biological activity is hot spots of organometallic chemistry.Polycarboxylic acid ligands have complex and variable coordination behaviors,which play an important role in forming new coordination mode and constructing metal-organic framework.Furthermore,studies have shown that biological activity can be improved by introduced selenium into organotin derivatives.Given the aforementioned considerations,we synthesized dicarboxylic acids and selenoacetic acids organic tin compounds,and its structure and properties are also detailed in this research.The main works of this paper are displayed as below.1.We took 1,3,4-thiadiazole-2,5-dithiol as raw materials,synthesized a?1,3,4-thiadiazole-2,5-diyldithio?diacetic acid ligand,and investigated the reactions of di and triorganotin substrates with the ligand.Five novel organotin?IV?complexes were prepared and characterized by X-ray diffraction.The results indicated that:?1?a 2:1 ratio reaction of Me₃SnCl with ligand obtained 1D pipeline-like and 1D ladder chain structure,respectively,while a reaction of?n-Bu₃Sn?₂O with ligand in 1:1 molar ratio afforded a 2D corrugated structure coordination polymer;?2?a reaction of R₂SnCl₂?R=Me;n-Bu?with ligand in 1:1 molar ratio afforded structure monomer with ladder as well as 1D infinite chain structure,respectively.Furthermore,the in vitro cytotoxicity investigation of complexes 1,3 and 4,against lung cancer cells?A549?and human cervix cell lines?HeLa?,were carried out with MTT-based assays.The obtained results presented that three organotin dicarboxylates exhibit outstanding inhibitory efficiency than cisplatin and complex 3 exhibits the highest activity among them.2.Investigations on the reactions of triorganotin substrates with two ligands—1,3-adamantanedicarboxylic acid and 2,6-naphthalenedicarboxylic acid obtained four organotin?IV?complexes,and a series of characterizations were also conducted.The analysis revealed that:?1?a 2:1 reaction of Me₃SnCl with ligands afforded infinite 2D network structure;?2?a 2:1 reaction of Ph₃SnCl with ligands afforded monomers.The screening test of complexes 6 and 7 against A549 and Hela were carryed out by means of MTT-based assays.The outcomes exhibited that these two complexes display outstanding inhibitory efficiency on two cancer cells,and complex 7 exhibits the highest activity among them,higher than the cisplatin.3.We investigated the reactions of 6,6?-dithionicotinic acid ligand with dimethyltin dichloride and different N-donor ligands by employing a slow diffusion procedure.Two novel organotin?IV?complexes 10-11 were prepared and characterized.The analysis revealed that:when N-donor ligand is 4,4?-bipyridine,the product is a 2D wavelike polymeric structure which is built by the interlinking of hexanuclear hexagonal78-membered macrocycles;when N-donor ligand is 1,10-phenanthroline,the product displays 1D right-handed helical chain.4.We synthesized two se-containing ligands—3,4-dimethyl-phenylselenoacetic acid and 4-fluorophenylselenoacetic acid,and reacted with alkyl tin.Five novel organotin?IV?complexes were synthesized and characterized.The structural analysis revealed that:?1?when the ligand reacted with trimethyltin chloride in 1:1 molar ratio,we obtained 1D infinite polymeric chain;?2?a reaction of the ligand with R₂SnCl₂?R=Me;n-Bu?in 2:1molar ratio afforded two kinds of monomers;?3?when ligands reacted with phenyltin,we acquired a drum-like structure;when phenyltin is replaced by n-BuSn?O?OH,we also got a a drum-like structure.