{closo-1,2-Me2-3-(η-Me3SiC2D)-3-(CO)-8,3(σ:η2-C(H)C(D)SiMe3)-3,1,2-MoC2B9H8} | 158402-40-5

• 英文名称: {closo-1,2-Me2-3-(η-Me3SiC2D)-3-(CO)-8,3(σ:η2-C(H)C(D)SiMe3)-3,1,2-MoC2B9H8}
• CAS: 158402-40-5
• 化学式: C₁₅H₃₅B₉MoOSi₂
• 分子量: 482.836
• InChiKey: RWEWVQOAZXSPJD-YXMHCHSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 (N(PPh3)2)(closo-1,2-Me2-3-(η3-C3H5)-3,3-(CO)2-3,1,2-MoC2B9H9) 、 乙炔基-2-D-三甲基-硅烷 以 乙醚 、 二氯甲烷 为溶剂， 生成 {closo-1,2-Me2-3-(η-Me3SiC2D)-3-(CO)-8,3(σ:η2-C(H)C(D)SiMe3)-3,1,2-MoC2B9H8}
  参考文献：
  名称：

  Alkyne–carbaborane coupling at a molybdenum centre: crystal structure of [closo-3,3,3-(CO)₃-8,3-{σ:η²-C(H)C(H)-SiMe₃}-3,1,2-MoC₂B₉H₁₀]

  摘要：

  In CH2Cl2 the complex [closo-1,2-Me2-3-(eta-PhC2Ph)-3-(CO)-3-(PPh3)-3,1,2-MoC2B9H9] decomposed to yield a mixture of [closo-1,2-Me2-3,3,3-(CO)3-3-(PPh3)-3,1,2-MoC2B9H9] and [closo-1,2-Me2-3,3-(CO)2-3-(PPh3)-8,3-{sigma:eta2-C(Ph)=C(H)Ph}-3,1,2-MoC2B9H8]. Protonation (HBF4.Et2O) of [NEt4][closo-3-(eta-C3H5)-3,3-(CO)2-3,1,2-MoC2B9H11], in CH2Cl2 at -78-degrees-C, in the presence of an excess of Me3SiC=CSiMe3, afforded a chromatographically separable mixture of [closo-3,3-(eta-Me3SiC2SiMe3)2-3-(CO)-3,1,2-MoC2B9H11] and [closo-3,3,3-(CO)3-8,3-{sigma:eta2-C(H)=C(H)SiMe3}-3,1,2-MoC2B9H10]. The latter complex forms via the intermediacy of Me3SiC=CH, generated by HF cleavage of Me3SiC=CSiMe3, and its structure was established by X-ray diffraction. The molybdenum atom is ligated on one side by three CO groups, and on the other by the open pentagonal face of the nido-1,2-C2B9 cage framework. The boron atom located in the beta site with respect to the two carbons carries a vinyl substituent C(H)=C(H)SiMe3, and this exopolyhedral group is eta2 co-ordinated to the molybdenum atom [Mo-C 2.43(1) and 2.55(1) angstrom]. Treatment of [N(PPh3)2][closo-1,2-Me2-3-(eta-C3H5)-3,3-(CO)-3,1,2-MoC2B9H9] and Me3SiC=CH with HBF4.Et2O gives initially the complex [closo-1,2-Me2-3,3-(eta-Me3SiC2H)2-3-(CO)-3,1,2-MoC2B9H9], which subsequently rearranges to [closo-1,2-Me2-3-(eta-Me3Si-C2H)-3-(CO)-8,3-{sigma:eta2-C(H)=C(H)SiMe3}-3,1,2-MoC2B9H8]. Use of Me3SiC=CD in this synthesis, combined with NMR studies, suggests that insertion of the alkyne into the cage B-H bond proceeds via the intermediacy of a molybdenum vinylidene species. The NMR data (H-1, C-13-{H-1}, B-11-{H-1}, and P-31-{H-1}) for the new compounds are reported and discussed in relation to the structures proposed.

  DOI：

  10.1039/dt9930003551