新型离子型有机锡化合物的合成及[(i-Pr)2NH2][(PhCH2)3Sn(μ~2-SCH2COO)]的晶体结构  

Synthesis of New Tin(Ⅳ) Complexes and Crystal Structure of [( i-Pr)_2NH_2][(PhCH_2)_3Sn(μ~2-SCH_2COO) ]

作　　者：钟桂云[1] 孙丽娟[2] 谢庆兰[2] 

机构地区：[1]江门职业技术学院材料技术系,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：《高等学校化学学报》2010年第11期2218-2221,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20372035)资助

摘　　要：在有机胺存在下,通过(PhCH2)3SnCl与HSCH2COOH反应得到了一系列五配位阴离子型有机锡化合物,分子结构通式为[Q][(PhCH2)3Sn(μ2-SCH2COO)][Q=H2NEt2(1),H2N(i-Pr)2(2),HN(n-Pr)3(3),HN(n-Bu)3(4)和H2PhNCH3(5)],并通过IR、1H NMR及元素分析等手段对所合成的化合物进行了表征.测定了[(i-Pr)2NH2][(PhCH2)3Sn(μ2-SCH2COO)](2)的晶体结构.结果表明,分子由1个一价阴离子和异丙基胺阳离子组成.锡原子为变形的三角双锥结构,氧原子和碳原子处于竖直轴上.阴阳离子之间通过氢键相连接,氮原子和氧原子之间的距离为0.2827 nm.The study of ionic organotin compounds is of current attention due 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 was synthesized 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;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 induced by ligand containing S has prompted us to investigate the reaction of organotin choride in some details.With this in mind,a series of new ionic organotin（Ⅳ） complexes with general formula [Q][（PhCH2） 3Sn（μ2-SCH2COO） ][Q = diethylammonium（1）,di-i-propylamrnonium（2）,tripropylammo-nium（3）,tri-n-butylammonium（4）,methylphenylammonium（5） ]was synthesized by the reaction of mercap-toacetic acid with tribenzyltin chloride in the presence of an organic base in this paper.These complexes were characterized by elemental analysis,IR and 1H NMR spectroscopies.The crystal structure of [（i-Pr） 2.NH2][（PhCH2） 3Sn（μ2-SCH2COO） ]was determined by X-ray crystallography.The structure consists of an anion part,in which the tin atom has a cis-tbp geometry with the O atom and C atom occupying the axial pos-tions,and a tri-n-propylammonium cation part;these two parts are connected through a hydrogen bond be-tween the N atom in the ammonium and the O atom of the carbonyl group with a N—O length of 0.2827 nm.

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]