化学学报 ›› 1995, Vol. 53 ›› Issue (8): 816-821. 上一篇    下一篇

研究论文

四羰基双[2,5-二(三甲硅基)-1-甲基环戊二烯基]

孔垂华;徐善生;周秀中   

  1. 华南农业大学生态研究室;南开大学化学系
  • 发布日期:1995-08-15

Synthesis and reactivities of tetracarbonyl Bis-[2,5-di(trimethylsilyl)-1-methylcyclopentadienyl] di-iron

KONG CHUIHUA;XU SHANSHENG;ZHOU XIUZHONG   

  • Published:1995-08-15

由甲基环戊二烯经两步类似反应向其环上引入两个Me3Si取代基, 生成(Me3Si)2-MeC5H3, 后者与Fe(CO)5反应除生成预期的双核Fe-Fe键产物[η^5-{Me3Si)2MeC5H2}Fe(CO)]2-(μ-CO)2(2)外, 还分离到小量单核化合物η^5-[(Me2Si)2MeC5H2]Fe(CO)2Cl(3), 2与碘反应生成Fe-Fe键断裂的单核铁碘化物(4)。2经Na/Hg还原生成Fe-Fe键断裂的铁负离子, 后者随即分别与数种氯化物反应, 生成在铁原子上引入相应取代基的铁衍生物η^5-[(Me3Si)2MeC5H2]Fe(CO)2R(R=PhCH2, 5; CH2COOC2H5, 6; Ph3Sn, 7; Ph2SnCl, 8)。测定了4的晶体结构, 晶体属单斜晶系, P21/c空间群, 晶胞参数a=0.7333(1), b=2.0089(3),c=1.3323(4)nm; β=92.02(2)°, V=1.962(1)nm^3, Z=4。

关键词: 红外分光光度法, 晶体结构, 环戊二烯 P, 铁络合物, 质子磁共振谱法, 三甲基硅烷类

2,5-Di(trimethylsilyl)-1-methylcyclopentadiene (1) was prepared by two similar reaction steps from methyl cyclopentadiene. The reaction of 1 and Fe(CO)5 gave the expected dinuclear product [η^5-{Me3Si)2MeC5H2}Fe(CO)]2-(μ-CO)2, (2). 2 reacted with iodine to yield the Fe-Fe bond cleaved iron iodide 4.2 was reduced by Na-Hg to form the Fe-Fe bond cleaved iron anion. The anion reacted respectively with some halides to afford the substituted iron derivatives η ^5-[(Me3Si)2MeC5H2]Fe(CO)2R (R=PhCH2, 5; CH2COOC2H5, 6; Ph3Sn, 7; Ph2SnCl, 8). The crystal structure of 4 was determined by X-ray crystallography. The crystal is monoclinic, space group P21/c with a=0.7333(1), b=2.0089(3), c=1.3323(4)nm; β=92.02(2)°, V=1.962(1)nm^3, Z=4, Dc=1.57g.cm^-^1.

Key words: INFRARED SPECTROPHOTOMETRY, CRYSTAL STRUCTURE, CYCLOPENTADIENE P, IRON COMPLEX, PROTON MAGNETIC RESONANCE SPECTROMETRY, TRIMETHYLSILANES

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