1.2-dicarba-closo-dodecaborano-tetrahydrofurane | 19610-39-0

• 英文名称: 1.2-dicarba-closo-dodecaborano-tetrahydrofurane
• 英文别名: μ-1,2-CH2OCH2-1,2-C2B10H10；1,2-CH2OCH2-1,2-C2B10H10
• CAS: 19610-39-0
• 化学式: C₄H₁₄B₁₀O
• 分子量: 186.265
• InChiKey: LKRISFDXBVZWJR-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：

  1.2-dicarba-closo-dodecaborano-tetrahydrofurane 、 potassium hydroxide 以 水 为溶剂， 生成 K[7,8-CH2OCH2-7,8-C2B9H10]
  参考文献：
  名称：

  A restricted polyhedral rearrangement of an aminosubstituted 12-vertex ferratricarbollide

  摘要：

  The oxidation of anion [7,8-CH2OCH2-7,8-C2B9H10](-) with aqueous FeCl3 gives the 10-vertex nido-carborane 5,6-CH2OCH2-5,6-C2B8H10 in 23% yield. Its interaction with BuNC in the presence of proton sponge gives the tricarbollide anion [7,8-CH2OCH2-9Bu(t)NH-7,8,9-C3B8H8](-) (44% yield) having a short linkage between carbon atoms. Further photochemical reaction of this anion with [CpFe(C6H6)](+) is accompanied by room-temperature polyhedral rearrangement giving ferratricarbollide 1-Cp-2,3-CH2OCH2-9-(BuNH)-N-t-1,2,3,9-FeC3B8H8 (5) in 89% yield. The process involves the migration of the amino-substituted carbon atom, while the separation of two other carbons (observed for the non-linked analogue) is restricted by the CH2OCH2 bridge. DFT calculations of the hypothetical non-rearranged isomer 1-Cp-2-(BuNH)-N-t-1,2,3,4-FeC3B8H10 revealed its strongly distorted geometry with the C2-C3 distance (2.347 angstrom) being clearly non-bonding, thus explaining the mild conditions of the polyhedral rearrangement. The structure of 5 was confirmed by X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.03.007
• 作为产物：
  描述：

  1,2-bis(hydroxymethyl)-ortho-carborane 在 1,2-trifluoro-2-chloroethyldiethylamine 作用下， 以 neat (no solvent) 为溶剂， 以70%的产率得到1.2-dicarba-closo-dodecaborano-tetrahydrofurane
  参考文献：
  名称：

  Alkylation of aromatic hydrocarbons by 1-fluoromethyl-o,m-carboranes by the action of AlCl3

  摘要：

  DOI：

  10.1007/bf00956366

文献信息

• Pathway bifurcations in the cage rearrangement of metallacarboranes: experimental and computational evidence
  作者：Mikhail M. Vinogradov、Ivan D. Nesterov、Yulia V. Nelyubina、Alexander A. Pavlov

  DOI：10.1039/d0dt03538f

  日期：——

  stability was investigated. Two iridium complexes undergo a polyhedral rearrangement with the formation of more than one isomer. The structures of the new isomers were determined by a single crystal X-ray diffraction analysis and 11B1H}–11B1H} COSY NMR. A full isomerization scheme of the less thermally stable complex was proposed based on DFT calculations. According to this mechanism sequential downhill

  合成了13个具有共价键合的笼状碳原子的铑和铱的新金属碳硼烷络合物，并研究了它们的热稳定性。两种铱配合物经历了多面体重排，形成了不止一种异构体。通过单晶X射线衍射分析和11 B 1 H} –11 B 1 H} COZY NMR确定了新异构体的结构。基于DFT计算，提出了热稳定性较差的配合物的完全异构化方案。根据该机理，在反应路径中出现顺序的下坡和上坡分叉。每个分支负责新产品的形成。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.12, 4.10, page 108 - 154
  作者：

  DOI：——

  日期：——
• A New Series of Organoboranes. III. Some Reactions of 1,2-Dicarbaclovododecaborane(12) and its Derivatives
  作者：T. L. Heying、J. W. Ager、S. L. Clark、R. P. Alexander、S. Papetti、J. A. Reid、S. I. Trotz

  DOI：10.1021/ic50010a004

  日期：1963.12
• Neocarboranes, a New Family of Stable Organoboranes Isomeric with the Carboranes
  作者：Daniel Grafstein、Joseph Dvorak

  DOI：10.1021/ic50010a011

  日期：1963.12
• Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)
  作者：Hao Shen、Hoi-Shan Chan、Zuowei Xie

  DOI：10.1021/om070128q

  日期：2007.5.1

  Interaction of [Me3NH][7,8-CH2OCH2-7,8-C2B9H10] with M(NR2)(4) gave the simple amine elimination products [eta(5)-(CH2OCH2)C2B9H9]M(NMe2)(2)(NHMe2) (M = Zr (2a), Hf (2b)) or the unexpected C-O bond cleavage products [sigma:eta(1):eta(5)-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me (3a), Et (3b)). The higher oxophilicity of the Ti center provides the driving force for the latter reactions. It is suggested that the C-O bond cleavage is prior to the amine elimination in the formation of 3a,b. This serves as a convenient and practical method for the preparation of constrained-geometry half-sandwich metallacarboranes with two different functional sidearms. Complex 3a can undergo a clean amine exchange reaction to produce new constrained-geometry titanacarborane amides. Reactions of 3a with unsaturated molecules CyNCNCy, SCS, Xyl-NC, PhCN, (BuNCS)-N-n, Ph2CCO, and PhNCO gave monoinsertion products. They, except for [sigma:eta(1):eta(5)-(OCH2)(Me2NCH2)C2B9H9]Ti[eta(3)-CyNC(NMe2)NCy] (7), do not react with amines. In sharp contrast, 7 can react readily with Me2NH to regenerate 3a and release guanidine, which leads to the discovery of new catalytic guanylation of amines. All new complexes were fully characterized by various spectroscopic techniques and elemental analyses. Most of them were further confirmed by single-crystal X-ray analyses.