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环戊二烯基铟(I)

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环戊二烯基铟(I)
识别
CAS号 34822-89-4  ✓
PubChem 85397242
ChemSpider 9270356
SMILES
InChI
InChIKey JZPXQBRKWFVPAE-UHFFFAOYSA-N
性质
化学式 C5H5In
摩尔质量 179.913 g·mol⁻¹
外观 乳白色固体
危险性
GHS危险性符号
《全球化学品统一分类和标签制度》(简称“GHS”)中易燃物的标签图案
《全球化学品统一分类和标签制度》(简称“GHS”)中有害物质的标签图案
GHS提示词 警告
H-术语 H228, H302, H315, H319, H335
P-术语 P210, P240, P241, P261, P264, P270, P271, P280, P301+312, P302+352, P304+340, P305+351+338, P312, P321
若非注明,所有数据均出自一般条件(25 ℃,100 kPa)下。

环戊二烯基铟(I),化学式为C5H5In,通常缩写为CpIn(Cp为环戊二烯基阴离子),是一种含有+1氧化态的有机铟化合物,具有半夹心结构的环戊二烯基络合物。它是第一个 (1957年 [1] ) 被发现报告的低价有机铟化合物。

制备和化学性质

环戊二烯基铟(I)可以轻易地通过氯化铟(I)与环戊二烯基锂反应制备: [2]

环戊二烯基铟(I)可与三氟化硼三氯化硼三溴化硼三碘化硼三甲基硼烷反应形成错合物,[3]例如:

在这些错合物中,环戊二烯基配体与铟原子的键合会从η5(π错合)变为η1(σ键合)。

含有+1氧化态的铟,具InX2-(X为卤素)阴离子的盐可由环戊二烯基铟(I)制备, 例如: [4]

结构和键结

环戊二烯基铟(I)固体是聚合物,为交替的铟原子和单元所形成的锯齿形链组成。两个铟原子与每个茂环的相对面相互作用,几乎垂直于环平面,而两个环与每个铟原子相互作用,形成约128°的键角。 [5]在气相中存在的环戊二烯基铟(I)单体中,铟原子位于芳族茂的中心轴上。

环戊二烯基铟(I)的键结研究表明,环戊二烯基阴离子的芳环电子会与铟的5s和5p原子轨道相互作用,而铟原子上的孤对电子是主要特征。[6]

InCp-chain-3D-balls.png
InCp-chain-3D-vdW.png
在环戊二烯基铟(I)的晶体结构中CpIn链的球棒空间填充模型

参考资料

  1. ^ Fischer E.O.; Hofmann H.P. Metall-cyclopentadienyle des Indiums. Angew. Chem. 1957, 69 (20): 639. doi:10.1002/ange.19570692008. 
  2. ^ Peppe C.; Tuck D.G.; Victoriano L. A simple synthesis of cyclopentadienylindium(I). J. Chem. Soc., Dalton Trans. 1981, 69 (12): 2592. doi:10.1039/DT9810002592. 
  3. ^ Contreras J. G.; Tuck D. G. Coordination compounds of indium. XXIII. Adducts of cyclopentadienylindium(I) with boron trihalides or trimethylboron. Inorganic Chemistry. 1973, 12 (11): 2596–2599. doi:10.1021/ic50129a021. 
  4. ^ Habeeb J.J.; Tuck D.G. Co-ordination compounds of indium. Part XXXI. Further studies of anionic complexes of indium(I). J. Chem. Soc., Dalton Trans. 1976, (10): 866–869. doi:10.1039/DT9760000866. 
  5. ^ Beachley O. T.; Pazik J. C.; Glassman T. E.; Churchill M. R.; Fettinger J.C.; Blom R. Synthesis, characterization and structural studies of In(C5H4Me) by x-ray diffraction and electron diffraction techniques and a reinvestigation of the crystalline state of In(C5H5) by x-ray diffraction studies. Organometallics. 1988, 7 (5): 1051–1059. doi:10.1021/om00095a007. 
  6. ^ Lin C.S. Tuck D.G. The electronic structure of cyclopentadienylindium. Can. J. Chem. 1982, 60 (6): 699–702. doi:10.1139/v82-103. 
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环戊二烯基铟(I)
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