高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (6): 898.

• 论文 • 上一篇    下一篇

1,1'-双(四甲基环戊二烯基)二茂铁与五羰基铁和三乙腈三羰基钼的反应

邓小斌, 徐善生, 王佰全, 周秀中   

  1. 1. 南开大学化学系, 元素有机化学国家重点实验室, 天津 300071;
    2. 中国科学院金属有机化学开放实验室, 上海 200032
  • 收稿日期:1999-08-25 出版日期:2000-06-24 发布日期:2000-06-24
  • 通讯作者: 周秀中(1930年出生),男,教授,博士生导师,从事金属有机化学研究.E-mail:zhouxz@public1.tpt.tj.cn E-mail:zhouxz@public1.tpt.tj.cn
  • 基金资助:

    国家自然科学基金(批准号:29972023);教育部博士点专项基金(批准号:9505502)

Reaction of 1,1'-Bis(tetramethylcyclopentadienyl)ferrocene with Pentacarbonyl Iron and Triacetonitrile Tricarbonyl Molybdenum

DENG Xiao-Bin, XU Shan-Sheng, WANG Bai-Quan, ZHOU Xiu-Zhong    

  1. 1. Depa rtment of Chemistry, Key Laboratoryof Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;
    2. Laboratoryof Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 20032, China
  • Received:1999-08-25 Online:2000-06-24 Published:2000-06-24

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摘要： 配体1,1'-双(四甲基环戊二烯基)二茂铁1,1'-Fc(Me4Cp)2(Ⅰ)与五羰基铁在二甲苯中回流反应,得二茂铁桥连双(四甲基环戊二烯基)四羰基二铁1,1'-Fc[(Me4Cp)Fe(CO)(μ-CO)]2(1).化合物1在氯仿中与单质碘反应,Fe_Fe键断裂,生成二茂铁桥连双铁碘化合物1,1'-Fc[(Me4Cp)Fe(CO)2I]2(2).配体与正丁基锂作用生成二茂铁桥连双(四甲基环戊二烯基负离子盐),后者随即与三乙腈三羰基钼反应形成1,1'-二茂铁双(四甲基环戊二烯基负离子盐)1,1'-Fc[(Me4Cp)Mo(CO)3-Li+]2(Ⅱ).钼负离子与CH3I作用在钼原子上发生甲基化,得到产物1,1'-Fc[(Me4Cp)Mo(CO)3Me]2(3).与BrCH2CH2Br反应,未得到预期的Mo_Mo键化合物,相反却得到少量亲核取代-消除的双钼-溴化合物1,1'-Fc[(Me4Cp)Mo(CO)3Br]2(4).经元素分析、IR及1HNMR表征化合物1—4的结构,并用X射线衍射测定了化合物1的晶体结构.

关键词: 1, 1-双(四甲基环戊二烯基)二茂铁, 二茂铁桥连双金属化合物, 富瓦烯, 晶体结构

Abstract: The xylene solution of 1,2-bis(tetramethylcyclopentadienyl)ferrocene, 1,1'-Fc(Me4Cp)2(Ⅰ) and Fe(CO)5 was refluxed for 10 h to yield ferrocene bridged bis(tetramethylcyclopentadienyl) tetracarbonyl, 1,1'-Fc[(Me4Cp)Fe(CO)2]2(1). Futher reaction of compound 1 with I2 in chloroform to yield Fe_Fe bond cleaved product, 1,1'-Fc[(Me4Cp)Fe(CO)2I]2(2). compound Ⅰ reacted sequentially with n BuLi and Mo(MeCN)3(CO)3 to generate 1,1'-Fcbis[tetramethylcyclopentadienyltricarbonyl molybdenum anion salt], 1,1'-Fc(Me4Cp)Mo(CO)3-Li+]2(Ⅱ). Futher reaction of compound Ⅱ with MeIyielded the corresponding methylmolybdenum complex, 1,1'-Fc[(Me4Cp)Mo(CO)3Me]2(3). The reaction of compound Ⅱ with BrCH2CH2Br did not gave the expected Mo_Mo binuclear compound, instead a small quantity of ferrocene bridged bis(molybdenum bromide) compound, 1,1'-Fc[(Me4CpMo-(CO)3Br]2(4), which was isolated by nucleophilic substitution and elimination mechanism. The molecular structures of compounds 1_4 were characterized by elemental analyses, IRand 1H NMRspectra. The crystal structure of compound 1 was determined by X-ray diffraction.

Key words: 1,1'-Bis(tetramethylcyclopentadienyl)ferrocene, Ferrocene-bridged bismetallic compound, Fulvalene, Crystal structure

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