3,6-Me2-1,2-closo-C2B10H10 | 862994-40-9

• 英文名称: 3,6-Me2-1,2-closo-C2B10H10
• 英文别名: 3,6-Me-1,2-C2B10H10
• CAS: 862994-40-9
• 化学式: C₄H₁₆B₁₀
• 分子量: 172.281
• InChiKey: UPQPSYNVQULXLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  3,6-Me2-1,2-closo-C2B10H10 、 3-Biphenylmagnesium bromide 在 cis-PdCl₂(P(C₆H₅)3)2 、 CuI 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到3,6-(biPh)2-1,2-closo-C2B10H10
  参考文献：
  名称：

  Designed Synthesis of New ortho-Carborane Derivatives: from Mono- to Polysubstituted Frameworks

  摘要：

  The use of nucleophilic and electrophilic processes allow the designed synthesis of several B-iodinated derivatives of o-carborane. Because of the straightforward Pd-catalyzed conversion of B-I to B-C bond with Grignard reagents, such as methylMgBr and biPhenylMgBr, both, symmetrical 3,6-R-2-1,2-closo-C2B10H10 and asymmetrical 3-1-6-Me-1,2-closo-C2B10H10 could be obtained. Not only conventional reactions in solution have been studied but also a highly efficient, clean and fast solvent-free procedure has provided successful results to regioselectively produce B-iodinated o-carborane derivatives by a careful control of the reaction conditions. The high number of nonequivalent leaving groups in boron iodinated o-carborane derivatives opens the possibility through B-C coupling to materials with novel possibilities and to self-assembling due to the enhanced polarizability of the C-H bond.

  DOI：

  10.1021/ic800362z

文献信息

• Are Methyl Groups Electron-Donating or Electron-Withdrawing in Boron Clusters? Permethylation of <i>o</i>-Carborane
  作者：Francesc Teixidor、Gemma Barberà、Albert Vaca、Raikko Kivekäs、Reijo Sillanpää、Josep Oliva、Clara Viñas

  DOI：10.1021/ja052981r

  日期：2005.7.1

  That methyl groups attached to carbon atoms are electron donors must not be generally assumed. In boron clusters, Me groups on boron are electron withdrawing. At the B3LYP/6-31G* level of theory, it has been proven that the Mulliken charge on each boron after substitution of -H by -Me increases by +0.18 unit. This leads to a high build-up of positive charge upon permethylation, then hampering it. Experimentally

  一般不应假设与碳原子相连的甲基是电子供体。在硼簇中，硼上的 Me 基团是吸电子的。在 B3LYP/6-31G* 理论水平上，已经证明，-H 被 -Me 取代后，每个硼上的马利肯电荷增加了 +0.18 个单位。这导致全甲基化时正电荷大量积聚，然后阻碍它。在实验上，这通过 9-I0.707H0.293-12-Cl0.566H0.434-3,4,5,6,7,8,10,11-Me8-1,2-C2B10H2 的合成证明，在其中第 9 和 12 位首先被甲基化，然后被亲核试剂攻击。这通过在相同实验条件下但具有时间控制的 3,6,8,9,10,12-Me6-1,2-C2B10H6 的合成得到证实。