{closo-1,2-Me2-3,3,3-(CO)3-3-(PPh3)-3,1,2-MoC2B9H9} | 150499-82-4

• 英文名称: {closo-1,2-Me2-3,3,3-(CO)3-3-(PPh3)-3,1,2-MoC2B9H9}
• CAS: 150499-82-4
• 化学式: C₂₅H₃₀B₉MoO₃P
• 分子量: 602.724
• InChiKey: KXTZDVSELDYTFU-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  (N(PPh3)2)(closo-1,2-Me2-3-(η3-C3H5)-3,3-(CO)2-3,1,2-MoC2B9H9) 、 三苯基膦 在 四氟硼酸-二乙醚络合物 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以29%的产率得到{closo-1,2-Me2-3,3,3-(CO)3-3-(PPh3)-3,1,2-MoC2B9H9}
  参考文献：
  名称：

  平衡羰基膦膦碳硼烷中的立体效应和电子效应

  摘要：

  对文献结构[[（CO）（PPh 3）2 MC 2 B 9 H 11 ]和[（CO）2（PPh 3）MC 2 B 9 H 11 ]的结构分析表明，在[L 3 MC 2 B 9 H 11 ]金属碳硼烷CO的反式影响大于PPh 3的反式影响。这项研究扩展到[L 4 MC 2 B 9 H 11 ]系统，新的钼碳硼烷[3,3,3-（CO）3 -3-PPh 3-3,1,2-闭合碳-MoC 2乙9 ħ 11 ]（2），[1,2-ME 2 -3,3,3-（CO）3 -3-PPH 3 -3,1,2-闭合碳-MoC 2乙9 ħ 9 ]（3）和反式- [3,3-（CO）2 -3,3-（PPH 3）2 -3,1,2-闭合碳-MoC 2乙9 ħ 11 ] （4）已准备并充分表征。考虑到在exopolyhedral配体取向（ELO）的2证实，就反式影响而言，[L 4 MC 2 B 9 H 11 ]中的CO> PPh 3也是如此。通过笼内CH

  DOI：

  10.1002/ejic.201700492

文献信息

• Dossett, Stephen J.; Li, Sihai; Stone, F. Gordon A., Journal of the Chemical Society, Dalton Transactions
  作者：Dossett, Stephen J.、Li, Sihai、Stone, F. Gordon A.

  DOI：——

  日期：——
• 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]
  作者：Stephen J. Dossett、Sihai Li、Donald F. Mullica、Eric L. Sappenfield、F. Gordon A. Stone

  DOI：10.1039/dt9930003551

  日期：——

  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.