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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (10): 1639-1645. 上一篇    下一篇

研究论文

四甲基硅锗桥连双环戊二烯基及双(四甲基环戊二烯基)四羰 基二铁的合成、结 构及热重排反应

孙秀丽;王佰全;徐善生;周秀中;翁林虹   

  1. 南开大学化学系元素及金属有机国家重点实验室;中国科学院上海有机化学研究 所.上海(200032);中国科学院金属有机化学国家重点实验室
  • 发布日期:2001-10-15

Synthesis, structures and thermal rearrangement reaction of (Me2SiGeMe2)[(η^5-C5R4)Fe(CO)2]2(μCO)2(R=H,Me)

Sun Xiuli;Wang Baiquan;Xu Shansheng;Zhou Xiuzhong;Weng Linhong   

  1. Shanghai Inst Organ Chem., CAS.Shanghai(200032)
  • Published:2001-10-15

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711

被引次数

3

1,2-二氯四甲基硅锗烷分别与环戊二烯基锂及四甲基环戊二烯基锂反应得到两个新的双齿配体：C5H5Me2SiGeMe2C5H5(9)和C5HMe4Me2SiGeMe2C5HMe4(10).配体9和10分别与Fe(CO)5在二甲苯中加热生成四甲基硅锗桥连双环戊二烯基四羰基二铁(11)和四甲基硅锗桥连双(四甲基环戊二烯基)四羰基二铁(13).11和13均可发生热重排反应，生成[(η^5-C5R4)Fe(CO)2]2(μ-Me2Si)(μ-Me2Ge)(R=H,12;R=Me,14)。测定了化合物11,12,13及14的晶体结构，讨论了桥连四甲基环戊二烯基配体的位阻效应对其某些结构参数以及重排反应性的影响。

关键词: 环戊二烯P, 有机硅化合物, 有机锗化合物, 羰基化合物, 铁络合物, 晶体结构, 热重排反应

Two new bidentate ligands, C5H5Me2SiGeMe2C5H5 (9) and C5HMe4Me2SiGeMe2C5HMe4 (10) were prepared by the reaction of CiMe2 SiGeMe2Cl with cyclopentadienyl lithium and tetramethylcyclopentadienyl lithium, respectively. Ligands 9 and 10 reacted with Fe(CO)5 to yield the diiron complexes (Me2SiGeMe2)- [ (η^5-C5R4)Fe(CO)]2(μ-CO2)(R=H, 11; R=Me,13). Complexes 11 and 13 could form the products [(η^5-C5R4)Fe(CO)2]2(μ-Me2Si) (μ-Me2Ge) (R=H, 12; R=Me,14) by a novel intramolecular thermal rearrangement reaction. The crystal and molecular structures of complexes 11, 12,13 and 14 were determined by X-ray diffraction. The steric effect of the bridged tetramethylcyclopentadienly ligand on some structural data and the rearrangement reactivity was discussed.

Key words: CYCLOPENTADIENE P, ORGANO SILICON COMPOUNDS, ORGANO GERMANIUM, CARBONYL COMPOUNDS, IRON COMPLEX, CRYSTAL STRUCTURE

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