9,10-dicarba-closo-undecaborane(11) | 17764-84-0

• 英文名称: 9,10-dicarba-closo-undecaborane(11)
• 英文别名: closo-(2,3-C2B9H11)；closo-2,3-C2B9H11
• CAS: 17764-84-0
• 化学式: C₂H₁₁B₉
• 分子量: 132.408
• InChiKey: JLKWVKUJTKAGLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  9,10-dicarba-closo-undecaborane(11) 、 氘代乙腈 以 氘代乙腈 为溶剂， 生成 nido-10-(CD₃CN)-7,9-C₂B₉H₁₁
  参考文献：
  名称：

  Cage-closing reactions of the nido-carborane anion 7,9-C2B9H12− and derivatives; formation of neutral 11-vertex carboranes by acidification

  摘要：

  尼多硼烷盐 (Bu4N)(尼多-7,9-R,Râ²-7,9-C2B9H10)（R,Râ² = H; R,Râ² = Me; R,Râ² = Ph；R,Râ²＝H；R,Râ²＝Me；R,Râ²＝Ph；R＝Ph，Râ²＝Me）与 H2SO4 在常温下反应，得到 11-蝶形的闭合硼烷 2,3-R,Râ²-2,3-C2B9H9，产量很高（R,Râ²＝H；R,Râ²＝Me；R,Râ²＝Ph；R＝Ph，Râ²＝Me）。含有 1(6)-X-7,9-C2B9H11â 阴离子的盐与 H2SO4 反应生成 10-X-2,3-C2B9H10（X = Cl，I）的闭硼烷卤代衍生物，而 4-F-2,3-(p-FC6H4)2-2,3-C2B9H8 则由 (Bu4N)(3-F-7,9-(p-FC6H4)2-7,9-C2B9H9) 和 F3CSO3H 生成。在用 F3CSO3H 酸化含有 10-OEt-7,9-C2B9H11â 和 10-F-7,9-(p-FC6H4)2-7,9-C2B9H9â 的盐的过程中，笼中的乙氧基和氟化取代基会被消除，主要产物分别为 2,3-C2B9H11 和 2,3-(p-FC6H4)2-2,3-C2B9H9。用 H2SO4 与含有 8-Me-7,9-C2B9H11â 和 10-Me-7,9-C2B9H11â 阴离子的盐反应，可以得到 B-Me-2,3-C2B9H10 异构体的混合物。据认为，B-Me-2,3-C2B9H10 在溶液中具有通性，其主要成分是 4-Me-2,3-C2B9H10。通性阴离子 10(11)-endo-Me-7,9-C2B9H11â 与乙酸发生质子化反应后，得到的是中性的 nido-硼烷 11-Me-2,8-C2B9H12，而不是封闭的 B-Me-2,3-C2B9H10。在 GIAO-B3LYP/6-311G*//MP2/6-31G* 理论水平上，通过 ab initio/GIAO/NMR 组合方法确定了 11-vertex闭合硼烷和 B-甲基-nido-硼烷的分子几何结构。

  DOI：

  10.1039/b203920f
• 作为产物：
  描述：

  (Bu4N)(nido-7,9-C2B9H12) 在 H₂SO₄ 作用下， 以 苯 为溶剂， 以74%的产率得到9,10-dicarba-closo-undecaborane(11)
  参考文献：
  名称：

  Cage-closing reactions of the nido-carborane anion 7,9-C2B9H12− and derivatives; formation of neutral 11-vertex carboranes by acidification

  摘要：

  尼多硼烷盐 (Bu4N)(尼多-7,9-R,Râ²-7,9-C2B9H10)（R,Râ² = H; R,Râ² = Me; R,Râ² = Ph；R,Râ²＝H；R,Râ²＝Me；R,Râ²＝Ph；R＝Ph，Râ²＝Me）与 H2SO4 在常温下反应，得到 11-蝶形的闭合硼烷 2,3-R,Râ²-2,3-C2B9H9，产量很高（R,Râ²＝H；R,Râ²＝Me；R,Râ²＝Ph；R＝Ph，Râ²＝Me）。含有 1(6)-X-7,9-C2B9H11â 阴离子的盐与 H2SO4 反应生成 10-X-2,3-C2B9H10（X = Cl，I）的闭硼烷卤代衍生物，而 4-F-2,3-(p-FC6H4)2-2,3-C2B9H8 则由 (Bu4N)(3-F-7,9-(p-FC6H4)2-7,9-C2B9H9) 和 F3CSO3H 生成。在用 F3CSO3H 酸化含有 10-OEt-7,9-C2B9H11â 和 10-F-7,9-(p-FC6H4)2-7,9-C2B9H9â 的盐的过程中，笼中的乙氧基和氟化取代基会被消除，主要产物分别为 2,3-C2B9H11 和 2,3-(p-FC6H4)2-2,3-C2B9H9。用 H2SO4 与含有 8-Me-7,9-C2B9H11â 和 10-Me-7,9-C2B9H11â 阴离子的盐反应，可以得到 B-Me-2,3-C2B9H10 异构体的混合物。据认为，B-Me-2,3-C2B9H10 在溶液中具有通性，其主要成分是 4-Me-2,3-C2B9H10。通性阴离子 10(11)-endo-Me-7,9-C2B9H11â 与乙酸发生质子化反应后，得到的是中性的 nido-硼烷 11-Me-2,8-C2B9H12，而不是封闭的 B-Me-2,3-C2B9H10。在 GIAO-B3LYP/6-311G*//MP2/6-31G* 理论水平上，通过 ab initio/GIAO/NMR 组合方法确定了 11-vertex闭合硼烷和 B-甲基-nido-硼烷的分子几何结构。

  DOI：

  10.1039/b203920f

文献信息

• Recent studies on RR′S·C2B9H11 charge-compensated ligands
  作者：Oscar Tutusaus、Francesc Teixidor、Rosario Núñez、Clara Viñas、Reijo Sillanpää、Raikko Kivekäs

  DOI：10.1016/s0022-328x(02)01541-3

  日期：2002.9

  formerly described compounds 7,8-R,R′-10-L-7,8-C2B9H9 (R=R′=H, L=SMe2 (1), L=SEt2 (2) and L=S(CH2)4 (3)). They have been fully characterised using 1H-, 11B- and 13C-NMR spectroscopy. Their bridging proton resonances have been located for the first time. Individual sulfonium substituent contributions have been calculated that have permitted to establish a rule to predict its position in the 1H-NMR spectrum

  在本文中，我们报告了7,8-R，R'-10-L-7,8-C 2 B 9 H 9系列三个新的碳硼烷衍生物的合成（R = R'= H，L = SEtPh; R = CH 3，R'= H，L = SMe 2和L = SEt 2）以及先前描述的化合物7,8-R，R'-10-L-7,8-C 2 B 9的增强表征H 9（R = R'= H，L = SMe 2（1），L = SEt 2（2）和L = S（CH 2）4（3））。使用1 H-，11 B-和13 C-NMR光谱。他们的桥接质子共振是第一次发现。已计算出单独的sulf取代基贡献，可以建立一个规则来预测其在1 H-NMR光谱中的位置。1和3的晶体结构已首次解析。热解的1，2和3中在回流温度下的芳族溶剂，得到的相应的9 -取代的异构化经由衍生物和2,3-混合物闭合碳-C 2乙9 ħ 11通过消除SR 2。已证明该反应可通过方便地选择芳族溶剂，配体和
• Synthesis of novel substituted (3)-1,7-dicarbaundecaborate(12) ions from 1,8-dicarba-closo-undecaborane(11) and carbanions
  作者：M. Frederick Hawthorne、David A. Owen

  DOI：10.1021/ja01023a054

  日期：1968.10

  Abstract : The reaction of the B9C2H11 carborane and its C-substituted derivatives with carbanions, derived from a series of closo-carboranes by C-H ionization, react to form anions in which the two carborane systems are mutually bonded. The product anions are considered to be B-substituted derivatives of the (3)-1, 7-B9C2H12(-) ion. (Author)

  摘要 : B9C2H11 碳硼烷及其 C 取代衍生物与碳负离子反应，碳负离子是通过 CH 电离衍生自一系列闭碳硼烷，反应生成阴离子，其中两个碳硼烷系统相互键合。产物阴离子被认为是 (3)-1, 7-B9C2H12(-) 离子的 B-取代衍生物。（作者）
• Synthesis and structural characterization of pyrazole-bridged metalla-bis(dicarbollide) derivatives of cobalt, nickel, copper, and iron: models for venus flytrap cluster reagents
  作者：Aravamuthan Varadarajan、Stephen E. Johnson、Frank A. Gomez、Sarmistha Chakrabarti、Carolyn B. Knobler、M. Frederick Hawthorne

  DOI：10.1021/ja00049a035

  日期：1992.11

  The synthesis and characterization of a family of pyrazole-bridged metallacarborane clusters is described. These species serve as nonradioactive models for the corresponding radio-transition-metal carriers which are potentially useful for the antibody-mediated gamma-imaging or beta-therapy of tumors (Venus flytrap clusters). Both monofunctional and bifunctional chelate precursors were prepared from the reactions of the anions of pyrazole and 4-carbomethoxypyrazole, respectively, with 2 equiv of closo-1,8-C2B9H11. In each instance, meso- and dl-isomers of the pyrazole-bridged nido-carboranes were obtained. The diastereomers were then converted, in the presence of stoichiometric amounts of aqueous base, to the formal 7,9-bis(dicarbollide) anions. The metal ions Co3+, Ni3+, Cu3+, and Fe3+ were incorporated into the unsubstituted pyrazole derivative in aqueous media at pH 12-14, resulting in the mixed meso- and dl-metallacarborane derivatives of 7, 8, 9, and 10, respectively. The carbomethoxy pyrazole dicarbollide derivative was complexed with Co3+ and Co-57(3+) in a similar manner to produce mixed meso- and dl-cobaltacarborane derivatives of 11 and 12, respectively. All diastereomeric metallacarborane derivatives were separated by column chromatography or HPLC techniques and characterized by spectroscopic and electrochemical techniques. The molecular structures of dl-Co3+ (7a), dl-Ni3+ (8a), meso-Ni3+ (8b), meso-Cu3+ (9b), dl-Fe3+ (10a), and meso-Co3+ (11b) have been determined from single-crystal X-ray diffraction experiments, and the structures of the diastereomeric complexes are correlated with H-1 and B-11 FT NMR spectra. dl-7a crystallizes in the monoclinic space group P2(1)/c with a = 10.618 (1) angstrom, b = 13.366 (1) angstrom, c = 14.326 (2) angstrom, beta = 109.925 (3)-degrees, V = 1901 angstrom3, and Z = 4. dl-8a crystallizes in the orthorhombic space group Pnma with a = 13.6874 (7) angstrom, b = 15.8587 (8) angstrom, c = 11.2429 (6) angstrom, V = 2447 angstrom3, and Z = 4. meso-8b crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 7.2139 (5) angstrom, b = 13.404 (1) angstrom, c = 19.768 (2) angstrom, V = 1908 angstrom3, and Z = 4. meso-% crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 7.1854 (8) angstrom, b = 13.434 (2) angstrom, c = 19.980 (2) angstrom, V = 1925 angstrom3, and Z = 4. dl-10a crystallizes in the monoclinic space group P1(1)/c with a = 10.6926 (5) angstrom, b = 13.3320 (7) angstrom, c = 14.3288 (7) angstrom, beta = 110.081 (1)-degrees, V = 1952 angstrom3, and Z = 4. meso-11b crystallizes in the triclinic space group P1BAR with a = 9.966 (2) angstrom, b = 10.475 (2) angstrom, c = 17.134 (3) angstrom, alpha = 79.957 (7)-degrees, beta = 77.882 (7)-degrees, gamma = 74.732 (7)-degrees, V = 1674 angstrom3, and Z = 2. Spectroscopic and structural data for the bridged complexes are compared with those for the corresponding unsubstituted metallacarborane derivatives.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B Comp.SVol.1/3, 13.16.3, page 186 - 188
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• Rietz, R. R.; Schaeffer, R.; Walter, E., Journal of Organometallic Chemistry, 1973, vol. 63, p. 1 - 9
  作者：Rietz, R. R.、Schaeffer, R.、Walter, E.

  DOI：——

  日期：——