1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12) | 313478-71-6

• 英文名称: 1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12)
• 英文别名: 1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane；1,12-bis(ethynyl)-1,12-dicarbo-closo-dodecaborane；1,12-bis(ethynyl)-para-carborane；1,12-diethynyl-para-carborane；1,12-bis-ethynyl-p-carborane；bis-(ethynyl)-para-carborane
• CAS: 313478-71-6
• 化学式: C₆H₁₂B₁₀
• 分子量: 192.271
• InChiKey: RYOOQQXUDSBXIR-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：

  1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12) 、 Au(acetylacetonate)(P(C6H4OMe-4)3) 以 丙酮 为溶剂， 以64%的产率得到
  参考文献：
  名称：

  Alkynyl Gold(I) Rigid-Rod Molecules from 1,12-Bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12)

  摘要：

  Reactions of 1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12), 1,12-(HCdropC)(2)-1,12-C2B10H10 (diethynylcarborane, decH(2)), with gold complexes of type [Au(acac)L] (acac = acetylacetonate) gave the neutral digold complexes [(AuL)(2)(mu-dec)] [L = PPh3 (1), P(C6H4-OMe-4)(3) (2), C((NHBu)-Bu-t)(NEt2) (3)]. The neutral complex [((AuCNBu)-Bu-t)(2)(mu-dec)] (5) was obtained by adding (BuNC)-Bu-t to the complex [Au-2(mu-dec)](n) (4) resulting from the reaction of decH(2) with [AuCl(SMe2)] and NEt3. The anionic complex PPN[Au(decH)(2)] (6) (PPN = Ph3P=N=PPh3) was isolated from its mixture with (PPN)(2)[{Au(decH)}(2)(mu-dec)] (7) by reacting PPN[Au(acac)(2)] and decH(2) in 1:4 molar ratio. The rigid-rod structures of the digold compound 2.CH2Cl2 and the salt 6.CHCl3 were determined by X-ray crystallography.

  DOI：

  10.1021/om0304311
• 作为产物：
  描述：

  1,12-bis(trimethylsilylethynyl)-para-carborane 在 KOH 作用下， 以 甲醇 、 水 为溶剂， 以99%的产率得到1,12-bis(ethynyl)-1,12-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  Synthesis and structure of 1,12-diethynyl-para-carborane

  摘要：

  Base desilylation of the novel compound, 1,12-bis(trimethylsilylethynyl)-para-carbonate 1,12-(Me,SiC=C)(2)-1,12-C2B10H10, gave the previously unknown compound 1,12-bis(diethynyl)-para-carborane, 1,12-(HC=C)(2)-1,12-C2B10H10. In the structure of the latter carborane, determined by X-ray diffraction, the ethynyl substituents induce a distortion of the carborane icosahedron, lengthening the tropical B-B bonds. The structural parameters of the diethynyl carborane are compared with known structures of type 1,12-(XE)(2)B10H10 bearing substituents on antipodal sites particularly the isostructural and isoelectronic 1,12-B12H10(CO)(2). (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00351-x

文献信息

• Improved syntheses of bis(ethynyl)-para-carboranes, 1,12-(RCC)2-1,12-C2B10H10 and 1,10-(RCC)2-1,10-C2B8H8 (R=H or Me3Si)
  作者：Mark A. Fox、Thomas E. Baines、David Albesa-Jové、Judith A.K. Howard、Paul J. Low

  DOI：10.1016/j.jorganchem.2006.05.044

  日期：2006.9

  disposition of the chloride and carboranyl substituents across the double bonds. These vinyl carboranes can be converted to bis(ethynyl) carboranes, 1,12-(RCC)2-1,12-C2B10H10 and 1,10-(RCC)2-1,10-C2B8H8 (R = H or Me3Si), easily, and in high yields. These findings provide the most convenient routes to bis(ethynyl) carboranes from the commercially available carboranes, 1,12-C2B10H12 and 1,10-C2B8H10

  铜介导的12顶点和10顶点对位碳硼烷1,12-C 2 B 10 H 12和1,10-C 2 B 8 H 10与反式-1-碘-2-的交叉偶联反应氯乙烯制得双（反-2-氯乙烯）碳硼烷，1,12-（ClCHCH）2 -1,12-C 2 B 10 H 10和1,10-（ClCHCH）2 -1,10 -C 2 B 8 H 8分别具有良好的收率。两种化合物的分子结构均通过X射线晶体学测定，验证了跨双键的氯和碳硼烷基取代基的反式布置。这些乙烯基碳硼烷可以转化为双（乙炔基）碳硼烷1,1,2- （RCC）2 -1,12-C 2 B 10 H 10和1,10-（RCC）2 -1,10-C 2 B 8 H 8（R = H或Me 3 Si），容易获得，并且产率很高。这些发现为迄今报道的从市售的碳硼烷1,12-C 2 B 10 H 12和1,10-C 2 B 8 H 10生成双（乙炔基）碳硼烷提供了最方便的途径。
• Dinuclear acetylide-bridged ruthenium(<scp>ii</scp>) complexes with rigid non-aromatic spacers
  作者：Surabhi Naik、Synøve Ø. Scottwell、Hsiu L. Li、Chanel F. Leong、Deanna M. D'Alessandro、Leslie D. Field

  DOI：10.1039/c9dt04856a

  日期：——

  A series of dinuclear acetylide-bridged ruthenium complexes with rigid linkers 1,4-bicyclooctane and 1,12-p-carborane was synthesised and the metal-to-metal communication through the bridge was explored using cyclic voltammetry.

  一系列具有刚性连接剂1,4-双环辛烷和1,12- p -碳硼烷的二核乙炔桥联钌配合物被合成，并通过循环伏安法探索了桥连接通道中的金属间通讯。
• Synthetic and structural studies on C-ethynyl- and C-bromo-carboranes
  作者：Mark A. Fox、Audrey M. Cameron、Paul J. Low、Michael A. J. Paterson、Andrei S. Batsanov、Andr?s E. Goeta、David W. H. Rankin、Heather E. Robertson、Julien T. Schirlin

  DOI：10.1039/b517538k

  日期：——

  (R(G) = 0.053) a model with C(5v) symmetry refined to give a C[triple bond]C bond distance of 1.233(5) A. For R = Me3Si (R(G) = 0.048) a model with C(s) symmetry refined to give a C[triple bond]C bond distance of 1.227(5) A. Molecular structures of 1,12-Br2-1,12-C2B10H10, 1-HC[triple bond]C-12-Br-1,12-C2B10H10 and 1,12-(Me(3)SiC[triple bond]C)2-1,12-C2B10H10 were determined by X-ray crystallography. Substituents

  由C-单铜对氨基甲酸酯和1-溴-2-（三甲基甲硅烷基）制备高产的C-单乙炔基对亚甲硼烷1-Me（3）SiC [三键] C-1,12-C2B10H11乙炔，BrC [三键] CSiMe（3）。由具有1-溴-2-（三甲基甲硅烷基）乙炔的C，C'-双铜对-甲叉烷衍生物，BrC低产率制备1,12-（Me3SiC [三键] C）2-1,12-C2B10H10 [三键] CSiMe3，已经过重新研究，并确定了其他产品，包括C-单乙炔基-碳氢化合物1-Me3SiC [三键] C-1,12-C2B10H11和由笼-笼耦合产生的两笼组件。单乙炔基和二乙炔基产物的收率差异是由于1-RC [三键] C-12-Cu-1,12-C2B10H10与溴炔之间的偶合过程非常不利。笼碳C（1）上的乙炔基强烈影响笼碳在C（12）上的化学反应性-“对映效应”的第一个例子，影响对-碳环衍生物的合成。使用更容易制备的溴乙炔，1-溴
• Molybdenum Complexes of <i>C</i>,<i>C</i>-Bis(ethynyl)carboranes: Design, Synthesis, and Study of a Weakly Coupled Mixed-Valence Compound
  作者：Neil J. Brown、Hannah N. Lancashire、Mark A. Fox、David Collison、Ruth Edge、Dmitry S. Yufit、Judith A. K. Howard、Mark W. Whiteley、Paul J. Low

  DOI：10.1021/om1010353

  日期：2011.2.28

  mixed-valence complexes is complicated by the mixing of metal d and bridging ligand π orbitals, which often makes the assignment of metal oxidation states ambiguous. However, in the case of complexes based on the cycloheptatrienyl-ligated molybdenum fragment, Mo(dppe)(η-C7H7), the strong ring to metal π bonding and metal to ring δ back-bonding interactions stabilize four of the metal d orbitals, while

  金属d和桥联配体π轨道的混合使有机金属混合价配合物的设计和研究变得复杂，这常常使金属氧化态的分配变得模棱两可。然而，在配合物的基础上，环庚三烯基-连接的钼片段的情况下，钼（DPPE）（η-C 7 H ^ 7），强环金属π键和金属环δ背面键合相互作用稳定金属四d轨道，而d z 2轨道由于与C 7 H 7环的a型MO的填充相互作用而不稳定。当钼（DPPE）（η-C 7 H ^ 7）助剂与基于1,12-双（乙炔基）-1,12-碳硼烷的桥连配体，弱耦合（Robin和Day类II）混合价体系[MO（DPPE）（η -C 7 H 7）} 2 μ-1,12-（C≡C）2 -1,12-C 2 B 10 H 10 }] +（[ 2 ] +），具有确定的钼氧化态做好准备。[ 2 ] +的近红外区域展示了三个间隔电荷转移（IVCT）跃迁和两个较低强度的互构（或dd）跃迁，这些跃迁已通过光谱解卷积得以解决。与[
• Coordination-Driven Self-Assemblies with a Carborane Backbone
  作者：Hershel Jude、Hendrik Disteldorf、Sonja Fischer、Tim Wedge、Adam M. Hawkridge、Atta M. Arif、M. Frederick Hawthorne、David C. Muddiman、Peter J. Stang

  DOI：10.1021/ja053050i

  日期：2005.8.1

  The design and self-assembly of five new supramolecular complexes (a rectangle, a triangle, a hexagon, and two squares) are described. These assemblies incorporate carborane building blocks and were prepared in excellent yields (> 85%). The assemblies and building blocks were characterized with multinuclear NMR spectroscopy, electrospray ionization mass spectrometry, and elemental analysis. Isotopically resolved mass spectrometry data confirm the existence of the rectangle, triangle, and hexagon, and NMR data are consistent with the formation of all five assemblies. The X-ray structures of two linear carborane building blocks, 1,12-(4-C equivalent to C(C5H4N)(2)-p-C2B10H10 (1) and 1,12-(trans-(Pt(PEt3)(2)l)C equivalent to C)(2)-p-C2B10H10 (2), are reported: 1 is monoclinic, P2(1)/c, a = 10.6791(4) angstrom, b = 8.0091(14) angstrom, c = 11.6796(4) angstrom, beta = 107.8461(15)degrees, V = 950.89(5) angstrom(3), Z = 2; 2 is monoclinic, C2/c, a = 62.1128(10) angstrom, b = 22.0071(3) angstrom, c = 14.0494(2) angstrom, beta = 89.9411(8)degrees, V= 19204.4(5) A(3), Z = 16. Crystals of the linear linker 1 exhibit close pi-pi pyridine and pyridine-B (carborane) interactions, which are discussed.