Syntheses,Structures And Characterization Of Zirconocene And Organotin Compounds Based On The Aromatic Selenites

Selenium complexes,particularly organoselenium,have been shown to exhibit promising chemotherapentic properities,which have caused them to become hot spots in the studies of tumor prevention and therapy.Besides,the various architectures of zirconocene and organotins have invoked intense interest in the molecular materials community because of its great potential for application in biological activity and catalytic activity.It is significant to synthesis zirconocene and organotin complexes in searching organometallics.Based on organoselenium,zirconocene and organotin having biochemical activity,we choose areneseleninic acids with different substituent groups as ligand and react with bis(cyclopentadienyl)zirconium dichloride or alkyltin choride.The research of the paper as follows:1.Areneseleninic acids(2-thiopheneseleninic acid,benzeneseleninic acid,4-fluorobenzeneseleninic acid,3,4-difluorobenzeneseleninic acid,3,5-difluorobenzeneseleninic acid,3-trifluoromethylbenzenetelluronic acid)were synthesized,and their reactions with bis(cyclopentadienyl)zirconium dichloride were researched.Six zirconocene compounds were obtained through reaction.Results showed that(1)when the 4-fluorobenzeneseleninic acid react with the bis(cyclopentadienyl)zirconium dichloride,two products are obtained which co-crystallize.One of the products,which are the centrosymmetric 32-membered macrocycle,is formed by a Zr-C bond cleavage through the loss of CpH.The other product is simply a hydrolysis product of Cp2ZrCl2.The central zirconium atoms are all six coordinational distorted octahedron configuration in the macrocycle component,while the zirconium atom in four coordinated tetrahedron structures in hydrolysis product of Cp2ZrCl2.(2)When 2-thiopheneseleninic acid,benzeneseleninic acid,3,4-di-fluorobenzeneseleninic acid,3,5-di-fluorobenzeneseleninic acid,3-trifluoromethylbenzenetelluronic acid react with bis(cyclopentadienyl)zirconium dichloride,respectively,the product is monomer structure with three zirconium atoms core.2.Areneseleninic acids(2-thiopheneseleninic acid,1-naphthaleneseleninic acid,benzeneseleninic acid,3-fluorobenzeneseleninic acid,3,4-difluorobenzeneseleninic acid,3,5-difluorobenzeneseleninic acid,3,4,5-trifluorobenzeneseleninic acid)were synthesized,and their reactions with diorganotin or triorganotin chloride wree researched.Thirteen organotin compounds were obtained.The analysis revealed that:(1)when areneseleninic acids react with Me3 SnCl at 1:1 molar ratio,they adopt infinite 1D polymeric chain structure.(2)when areneseleninic acids react with Ph2SnCl2 in a molar of 2:1,obtained four tetranuclear cage structures.(3)when areneseleninic acids react with t-Bu2SnCl2 in a molar of 2:1,obtained seven four-membered Sn2O2 ring structures and one infinite 1D polymeric chain structure.3.The antitumor activities in vitro of part of new compounds were carried out based on the structures of these zirconocene and organotin compounds.The cell viability was determined by MTT dye uptake.Breast cancer cell lines(MDA-MB-231),human cervix cell lines(HeLa),human lung cancer(A549)were used to assay the cytotoxicity of the complexes and we have analyzed the results.