新型离子型有机锡化合物的合成及[H_2N(i-Pr)_2][(Ph_3Sn)_3(O_2CCH_2CO_2)_2]·CH_3CH_2OH晶体结构研究  

Synthesis of New Tin(Ⅳ) Complexes and Study of Crystal Structure of [(i-Pr)_2NH_2][(Ph_3Sn)_3(O_2CCH_2CO_2)_2]·CH_3CH_2OH

作　　者：钟桂云[1] 刘芳[1] 孙丽娟[2] 

机构地区：[1]江门职业技术学院材料技术系,广东江门529090 [2]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《湘潭大学自然科学学报》2010年第4期68-73,共6页Natural Science Journal of Xiangtan University

基　　金：国家自然科学基金项目(20372035)

摘　　要：在有机胺的存在下,（Ph）_3SnCl与HOOCCH_2COOH反应,得到了一系列的五配位阴离子型有机锡化合物,分子结构通式为：Q[（Ph_3Sn）_3（O_2CCH_2CO_2）_2]·CH_3CH_2OH（Q=HNR_3=H_2NEt_2（1）,HN（i-Pr）_2（2）,N（n-Pr）_3（3）,N（n-Bu）_3（4）,HN（（CH_2）_4CH_3）_2（5）,并通过IR,~1H NMR,元素分析对这些化合物进行了表征.测定了[（i-Pr）_2NH_2][（Ph_3Sn）_3（O_2CCH_2CO_2）_2]·CH_3CH_2OH（2）的晶体结构.结果表明,化合物由3个锡原子的单体组成,锡原子为三角双锥结构,晶胞参数a=1.426 3（10）nm,b=1.999 6（13）nm,c=2.318 84（16）nm,β=90°,Z=8.The study of ionic organotin compounds is of current attention owing to their diversified molecular structures and wide range of applications,such as biological activities and as catalysts in organic synthesis. In our preivous studies,A series of ionic organotin complexes were synthesisted by the reaction of organotin chloride with organic acid in the present of an organic base.In the reaction of triphenyltin chloride and mercaptoacetic acid in the presence of an organic base,an unexpected tin-carbon cleavage process was observed in the reaction;while the reaction of mercaptoacetic acid with diphenyltin dichloride or phenyltin trichloride in the presence of organic base generated no Sn-C cleavage products.Our interest in the mechanism of the tin-carbon cleavage of organotin has prompted us to investigate in some detail the reaction of organotin choride.With this in mind,A series of new ionic organotin（Ⅳ） complexes with general formula Q [（Ph_3Sn）_3（O_2CCH_2CO_2）_2]·CH_3CH_2OH（Q=diethylammonium,（1）,di-i-propylamrnonium（2）,tri-n-propylammonium （3）,tri-n-butylammonium（4）,dipentylammonium（5） ） were synthesized by the reaction of malonic acid with triphenyltin chloride in the presence of an organic base.The reaction generated no Sn-C cleavage products.These complexes have been characterized by elemental analyses,IR and ~1H NMR spectroscopies.The crystal structure of[（i-Pr）_2NH_2][（Ph_3Sn）_3（O_2CCH_2CO_2）_2]·CH_3CH_2OH was determined by X-ray crystallography.In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters of a =1.426 3（10） nm,b =1.999 6（13） nm,c = 2.318 84（16） nm,β=90°and Z=8.

关 键 词：五配位有机锡化合物 离子型有机锡 晶体结构 

分 类 号：O621.3[理学—有机化学]