高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (4): 501.

• 论文 • 上一篇    下一篇

二[氧合-二(4-二茂铁基苯甲酸二烷基锡(Ⅳ))]配合物的合成、谱学表征和晶体结构研究

卢文贯1, 陶家洵1, 王玉珍2, 吕扬3, 赵斌3, 郑启泰3   

  1. 1. 清华大学化学系, 北京 100084;
    2. 中国科学院化学研究所, 北京 100080;
    3. 中国医学科学院, 中国协和医科大学药物研究所, 北京 100050
  • 收稿日期:1999-06-30 出版日期:2000-04-24 发布日期:2000-04-24
  • 通讯作者: 陶家洵(1941年出生),男,双硕士,副教授,从事结构分析与核磁共振研究.

Synthesis, Spectroscopic Characterization of Bis-[oxo-bis(4-ferrocenylbenzoato dialkyltin(IV))] and Crystal Structural Studies of the Former Compound

LU Wen-Guan1, TAO Jia-Xun1, WANG Yu-Zhen2   

  1. 1. Department of Chemistry, Tsinghua University, Beijing 100084, China;
    2. Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, China;
    3. Instituteof Material Medical, The Chinese Academyof Medical Sciences, Peking Union Medical College, Beijing 100050, China
  • Received:1999-06-30 Online:2000-04-24 Published:2000-04-24

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被引次数

18

摘要： 合成了{[(n-Bu)2Sn(4-Fc-C6H4COO)]2O}2(1)和{[(n-Oct)2Sn(4-Fc-C6H4COO)]2O}2(2)(Fc=ferrocenyl)两种新的配合物,对其进行了元素分析,并用IR,NMR(1H,13C,119Sn)进行了谱学表征.单晶X射线衍射法测定表明,配合物1的晶体属单斜晶系,P21/c空间群,晶胞参数a=1.2988(1)nm,b=2.4655(1)nm,c=3.4506(1)nm,β=91.556(2)°,V=11.0454(1)nm3,Z=4,最终可靠因子Rf=0.071,Rw=0.070.分子1为具有一个Sn2O2四元中心内环的二聚结构,桥氧原子又各连接一个外环Sn原子,呈三配位.内环锡和外环锡采用略有不同的加帽三角双锥配位几何.4个羧酸酯基具有两种不同的配位方式,其中两个羧酸酯基通过其两个氧原子以桥式双齿分别跨接于一个内环锡和一个外环锡,而另外两个羧酸酯基则以单齿配位方式各与一个外环锡相连接.Sn2O2中心内环与苯甲酸酯基、茂环等共轭体系之间相互未能共平面.整个分子结构中无对称中心.

关键词: 二烷基锡羧酸酯, 二茂铁, 谱学表征, 晶体结构

Abstract: In this paper, the novel compounds { [( n Bu)2Sn(4 Fc C6H4COO)]2O}2(1) and { [( n Oct)2Sn(4 Fc C6H4COO)]2O}2(2)(Fc=ferrocenyl) have been synthesized and characterized by elemental analysis, IRand NMR( 1H, 13C and119Sn) spectroscopy. The crystal structure of compound 1 has been determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c . The cell parameters are: a =1.2988(1) nm, b =2.4655(1) nm, c =3.4506 (1) nm, β =91.556(2)°, V =11.0454(1) nm3, Z =4. The structure was refined to final Rf=0.071, Rw= 0.074 . Compound 1 is a dimer structure mode with a four-member central endo-cyclic Sn2O2 unit in which the bridged oxygen atoms are tri coordinated. Each bridged oxygen atom also connects an exo-cyclic tin atom. Both endo and exo-cyclic tin atoms are all five coordination and have coordination geometry of monocapped trigonal bipyramid with very similarly distorted mode. Four carboxylate ligands are divided into two types. Two of the carboxylate ligands are bidentate and bridging to each pair of exo-and endo-cyclic tin atoms by using both oxygen atoms. The others are monodentate and coordinate each exo-cyclic tin atom. When considering further the longer distance interactions between the carboxyl oxygen in carboxylate ligand and endo cyclic tin atom (0.2775—0.2866 nm) and between the ester oxygen in carboxylate ligand and exo-cyclic tin atom(0.2980—0.3006 nm), not only carboxylate ligand chelates to exo-cyclic tin by anisobidentate mode but also their ester oxygen itself is tricoordinated and bridges to both endo and exo-cyclic tin atoms. In compound 1, the coplanarity of two conjugate systems(benzoyloxy group and substituted Cp ring) is not good. And two conjugate systems can not be coplanar with the central endo cyclic Sn2O2 unit. Unlike the general compounds characteristic of { [R2Sn(O2CR′)]2O}2, there is no center of symmetry in the molecule structure of compound 1.

Key words: Dialkyltin carboxylate, Ferrocene, Spectroscopic characterization, Crystal structure

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