三(三甲基硅)环戊二烯与六羰基钼的反应

The Reaction of Tris (trimethylsilyl)cyclopentadiene with Hexacarbonyl Molybdenum

三（三甲基硅）环戊二烯与六羰基钼在二甲苯中回流8h，反应停留在生成中间物η5－［（Me3Si）nC5H5-n］Mo（CO）3H（n＝2，3）（Ⅰ）的阶段,不经分离，Ⅰ随即分别与CCI4·NBS及Mel反应，生成其相应的钼卤化物η5－［（Me3Si）nC5H5-n］Mo（CO）3X［n＝3，X＝CI（l），Br（2），I（3）；n＝2，X＝Cl（4），Br（5），I（6）］．4-6是由于茂环上脱掉1个Me3Si基．经元素分析和IR及1HNMR谱表征了化合物1-6的结构，并用X射线衍射测定了1的晶体结构．

The xylene solution of tris (trimethylsilyl)cyclopentadiene and Mo (CO)6 was refluxed for 8 h. The reaction was stopped at the formation of the intermediate, mononuclear molybdenum hydride η5-[(Me3Si)nC5H5-n]Mo (CO)3H (n=2, 3) (Ⅰ). The reaction can not proceed further to form the binuclear(Mo-Mo) product. It is probably due to the steric effect of three silyl groups which hindered the further progress of the reaction. Desilylation happened while the reaction was proceeding. Compound Ⅰ was not isolated from the xylene solution and reacted immediately with CCl4, NBS and MeI respectively to give the corresponding molybdenum halides η5-[(Me3Si)nC5H5-n]Mc (CO),X [n=3; X: Cl(1), Br(2), I(3). n=2; X: Cl(4), Br(5), I(6)]. Compounds 4, 5, and 6 are desilylation products. The molecular structures of 1-6 were characterized by elemental analyses, IR and 1H NMR spectra. The crystal structure of 1 was determined by X-ray diffraction.