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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (10): 938-942. 上一篇    下一篇

研究论文

含金属基团的四价锡化合物的合成和取代反应动力学

王序昆;刘向阳;张正之;梁树森   

  1. 南开大学元素有机化学研究所;南开大学化学系
  • 发布日期:1987-10-15

The synthesis and substitution kinetics of Tin(IV) compounds with attached metal groups

WANG XUKUN;LIU XIANGYANG;ZHANG ZHENGZHI;LIANG SHUSEN   

  • Published:1987-10-15

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651

被引次数

2

通式为[Fe(CO)~2Cp]~2Sn(Ar)Cl的化合物为一组新的化合物,由[Fe(CO)~2Cp]~2SnCl2与AgMgX反应合成.[Fe(CO)~2Cp]~2Sn(Ar)Cl与各种亲核试剂Y发生取代反应给出另一组新的化合物[Fe(CO)~2Cp]~2Sn(Ar)Y,其中[Fe(CO)~2Sn(p-MeC~6H~4)Br经X射线衍射分析确定结构.[Fe(CO)~2Cp]~2Sn(1,3,5-Me~3C~6H~3)Cl与NAS~2CNMe~2或KSCN在不同溶剂中的反应动力学表明,由于锡易形成高配位中间体,尽管锡上两个较大的金属基团带来一定空间障碍,反应仍主要按SN2机理进行.

关键词: 晶体结构测定, 反应机理, 反应动力学, Ｘ射线衍射分析, 取代反应, 环戊二烯 P, 羰基络合物, 锡化合物, 格氏试剂, 四配位

A series of new compounds with the general formula [Fe(CO)2Cp]2SnRCl [R = (un)substituted Ph, Cp = h5-C5H5] was prepared from the reaction of [Fe(CO)2Cp]2SnCl2 with RMgX (X = halide). The reaction of [Fe(CO)2Cp]2SnRCl with a series of nucleophiles, Y-, gave another group of new compounds, [Fe(CO)2Cp]2SnRY, among which [Fe(CO)2Cp]2Sn(p-MeC5H4)Br was characterized by an x-ray structural anal. The kinetics of the reaction between [Fe(CO)2Cp]2Sn(2,4,6-Me3C6H2)Cl and NaS2CNMe2 or KSCN in different solvents showed that the major reaction pathway was SN2 despite the steric hindrance from the two bulky iron groups attached to the central tin.

Key words: CRYSTAL STRUCTURE DETERMINATION, REACTION MECHANISM, REACTION KINETICS, X-RAY DIFFRACTION ANALYSIS, SUBSTITUTION REACTION, CYCLOPENTADIENE P, CARBONYL COMPLEX, TIN COMPOUND, GRIGNARD REAGENT, TETRACOORDINATE

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