高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (9): 1400.

• 论文 • 上一篇    下一篇

(四甲基二硅撑)双(3-三甲硅基环戊二烯基)-四羰基二铁的反应性

孔垂华1, 徐善生2, 周秀中2   

  1. 1. 华南农业大学生态研究所, 广州, 510642;
    2. 南开大学化学系, 天津, 300071
  • 收稿日期:1994-10-06 修回日期:1995-03-15 出版日期:1995-09-24 发布日期:1995-09-24
  • 通讯作者: 周秀中
  • 作者简介:孔垂华,男,31岁,博士,讲师.
  • 基金资助:

    国家自然科学基金;南开大学元素有机化学实验室开放基金

Reactivity of Tetramethyldisilandiyl Bis(3-trimethylsilylcyclopentamenyl)-tetracarbonyl Diiron

KONG Chui-Hua1, XU Shan-Sheng2, ZHOU Xiu-Zhong2   

  1. 1. Institute of Ecology, South China Agricultural University, Guangzhou, 510642;
    2. Department of Chemistry, Nankai University, Tianjin
  • Received:1994-10-06 Revised:1995-03-15 Online:1995-09-24 Published:1995-09-24

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被引次数

3

摘要： 标题化合物(Me2SiSiMe2)[η5-(3-Me3SiC5H3)Fe(CO)2]2/(μ-CO)2(A)分子中的Fe-Fe键被钠汞齐还原断裂,生成相应的双铁负离子,分别与MeCOCl、PhCOCl、PhCH2Cl、ClCH2COOC2H5和Ph3SnCl进行亲核取代反应,生成在铁原子上引入相应取代基的产物(Me2SiSiMe2)[η5-(3-Me3SiC5H3)Fe(CO)2R]2(R:MeCO(1),PhCO(2),PhCH2(3),CH2COOC2H5(4),Ph3Sn(5),I(6)).A在氯仿中与碘反应,得到Fe-Fe断裂的双铁碘化物,但在苯中与过量碘反应,则得到Fe-I+-Fe桥联的离子型化合物(Me2SiSiMe2)[η5-(3-Me3SiC5H3)Fe(CO)2]2I+·I3-(7).化合物6的晶体和分子结构经X射线衍射测定,6属单斜晶系,P21/c空间群,a=1.7217(4)nm,b=0.7753(2)nm,C=1.3629(7)nm,β=103.80(3)°,V=1.767(2)nm3,Z=4,Dc=1.6299·cm-1,最终偏差因子R=0.054.

关键词: 反应性, Fe-Fe键断裂, 分子结构, 亲核取代反应

Abstract: The Fe-Fe bond of the title compound(Me2SiSiMe2)[η5-(3-Me2SiC5H3)Fe(CO)]2(μ-CO)2(A) was cleaved by sodium amalgam and the corresponding bis (iron anion) was produced, The nucleophilic reaction of the anion with MeCOCl,PhCOCl,PhCH2Cl, ClCH2COOC2H5and Ph3SnCl gave respectively the alkylation, acylation and metallation products (Me2SiSiMe2)[η5-(3-Me3SiC5H3)Fe(CO)2R]2(R: CH3CO(1), PhCO(2) PhCH2(3), CH2COOC2H5(4),Ph3Sn(5)),The Fe-Fe bond was also (4) cleaved by iodine in chloroform and resulted in forming iron iodide (Me2SiSiMe2)[η5-(3- Me3SiC5H3)Fe(CO)2I]2:(6). However the reaction of Awith iodine in benzene yielded Fe-I+-Fe bridged ionic compound (Me2SiSiMe2)[η5-(3-Me3SiC5H3)Fe(CO)2]2I+·I3-(7).The crystal structure of 6 was determined by X-ray diffraction. The crystal is monoclinic, space group P21/c with a=1. 7217(4) nm,b=0.7753(2) nm,c=1. 3629(7)nm,β=103. 80(1)°,V=1.767(2)nm3,Z=4, Dc= 1.629g/cm3.The final deviation factor R=0.054.

Key words: Reactivity, Cleavage of Fe-Fe bond, Molecular structure, Nucleophilic substitution

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