1,7-diphenyl-1,7-dicarba-closo-dodecaborane(12) | 17805-18-4

• 英文名称: 1,7-diphenyl-1,7-dicarba-closo-dodecaborane(12)
• 英文别名: 1,7-diphenyl-meta-carborane
• CAS: 17805-18-4
• 化学式: C₁₄H₂₀B₁₀
• 分子量: 296.423
• InChiKey: BQUBJASMMHZGHU-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：

  1,7-diphenyl-1,7-dicarba-closo-dodecaborane(12) 在 硫酸 、 硝酸 作用下， 以 四氯化碳 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  Sergeev, V. A.; Kalinin, V. N.; Shitikov, V. K., Journal of general chemistry of the USSR, 1981, vol. 51, p. 716 - 720

  摘要：

  DOI：
• 作为产物：
  描述：

  二苯基邻碳硼烷 以 neat (no solvent) 为溶剂， 生成 1,7-diphenyl-1,7-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  Redetermination of 1,7-Diphenyl-1,7-dicarba-closo-dodecaborane(12)

  摘要：

  The previous determination of the structure of the title molecule, C14H20B10 [Astakhin, Romanov, Gusev, Kalinin, Zakharkin & Los (1977). Zh. Strukt. Khim. 18, 406-408] with R = 0.15 has been superseded by the present determination which has R = 0.06.

  DOI：

  10.1107/s0108270196002107

文献信息

• C-arylation and C-heteroarylation of icosahedral carboranes via their copper(I) derivatives
  作者：Robert Coult、Mark A. Fox、Wendy R. Gill、Penelope L. Herbertson、J.A.Hugh MacBride、Kenneth Wade

  DOI：10.1016/0022-328x(93)83337-u

  日期：1993.12

  product. Cyclic or linear arylene coupled systems are obtained when di-iodoarenes are used. Copper(I) derivatives may be generated from C-unsubstituted or C-monosubstituted carboranes using copper(I) t-butoxide when substituents incompatible with the use of C-lithio-intermediates are involved. The C-copper(I) derivative of 1,2-dicarba-closo-dodecaborane(12) gives 1,2-di-2′-pyridyl-1,2-dicarba-closo-dodecaborane(12)

  的1,2-，1,7-，或1,12- dicarba- C-单-或C，C'-二-铜（1）的衍生物之间的反应闭合碳在存在-dodecaborane（12）和芳基碘吡啶，得到相应的C-单-或C，1,7-的和C'-二芳基衍生物1,12- dicarba-闭合碳-dodecaboranes（12）; 1,2- dicarba-闭合碳-dodecaborane（12）给出仅C-单芳基产物。当使用二碘芳烃时，获得环状或线性亚芳基偶联的系统。当涉及到与使用C-硫代中间体不相容的取代基时，可以使用叔丁醇铜从C-未取代或C-单取代的碳硼烷生成铜（I）衍生物。1,2- dicarba-的C-铜（I）衍生物闭合碳-dodecaborane（12）给出了1,2-二2'-吡啶基-1,2- dicarba-闭合碳-十二烷基硼烷（12），特别是带有2-溴吡啶的。的（推断）中间体单-2-吡啶基-衍生物，从2-乙炔基吡啶和二
• Synthesis and reactivity of 7,9-diphenyl-nido-carbaundecaboranes: rearrangement processes in carbaplatinaboranes revisited
  作者：Alan J. Welch、Andrew S. Weller

  DOI：10.1039/a607523a

  日期：——

  A number of synthetic routes towards diphenyl nido-carbaborane [7,9-Ph 2 -7,9-nido-C 2 B 9 H 10 ] - have been elucidated. Base-induced degradation of 1,7-Ph 2 -1,7-closo-C 2 B 10 H 10 afforded two isolable products [NEt 3 H][7,9-Ph 2 -x-OEt-7,9-nido -C 2 B 9 H 9 ] (x = 3 1a or 2 1b), both of which contain an ethoxide-substituted cage. The structural identity of 1a was established by a single-crystal X-ray diffraction study. Fluoride-induced degradation gave a product assigned as [NBu 4 ][7,9-Ph 2 -10-OH-7,9-nido-C 2 B 9 H 9 ] 2, also studied crystallographically. Heating a solid sample of Cs[7,8-Ph 2 -7,8-nido-C 2 B 9 H 10 ] in a sealed tube under vacuum for 4 h at 300 °C afforded the target species [NEt 3 H][7,9-Ph 2 -7,9-nido-C 2 B 9 H 10 ] 3, after cation metathesis. Deprotonation of 3 and reaction with [PtCl 2 (PMe 2 Ph) 2 ] afforded the new compound 1,1-(PMe 2 Ph) 2 -2,4-Ph 2 -1,2,4-closo -PtC 2 B 9 H 9 4. Compound 4 has been characterised by multinuclear ( 1 H, 11 B and 31 P- 1 H}) NMR spectroscopy as well as a single-crystal X-ray diffraction study. The isolation of this stable (in refluxing toluene) compound having a 1,2,4-MC 2 B 9 cage architecture indicates that a hextuple-concerted diamond–square–diamond mechanism cannot be operating in the spontaneous isomerisation of 1,2-Ph 2 -3,3-(PMe 2 Ph) 2 -3,1,2-closo -PtC 2 B 9 H 9 below ambient temperature to afford 1,1-(PMe 2 Ph) 2 -2,8-Ph 2 -1,2,8-closo -PtC 2 B 9 H 9 . The new compounds 1,1-(PR 3 ) 2 -2,4-Ph 2 -7-OEt-closo -1,2,4-PtC 2 B 9 H 8 (R 3 = Me 2 Ph 5a or Et 3 5b), both fully characterised by multinuclear NMR spectroscopy, have also been synthesized.

  已经阐明了多种合成二苯基nido-卡巴烯的路线[7,9-Ph₂-7,9-nido-C₂B₉H₁₀]。通过碱引起的1,7-Ph₂-1,7-closso-C₂B₁₀H₁₀的降解，获得了两个可分离的产物[NEt₃H][7,9-Ph₂-x-OEt-7,9-nido-C₂B₉H₉](x = 3或2)，这两者都含有一个乙氧基取代的笼结构。通过单晶X射线衍射研究确定了1a的结构身份。氟离子引起的降解得到了一个产物，被赋予为[NBu₄][7,9-Ph₂-10-OH-7,9-nido-C₂B₉H₉] 2，也通过晶体学进行了研究。在真空中封闭管内将Cs[7,8-Ph₂-7,8-nido-C₂B₉H₁₀]固体样品加热4小时至300°C，获得了目标物种[NEt₃H][7,9-Ph₂-7,9-nido-C₂B₉H₁₀] 3，经过阳离子交换反应。3的去质子化反应与[PtCl₂(PMe₂Ph)₂]反应，得到了新化合物1,1-(PMe₂Ph)₂-2,4-Ph₂-1,2,4-closso-PtC₂B₉H₉ 4。化合物4通过多核（¹H, ¹¹B和³¹P-¹H}) NMR光谱以及单晶X射线衍射研究进行了表征。该稳定化合物在回流甲苯中能够独立存在，其具有1,2,4-MC₂B₉笼架构，表明在环境温度以下1,2-Ph₂-3,3-(PMe₂Ph)₂-3,1,2-closso-PtC₂B₉H₉自发异构化为1,1-(PMe₂Ph)₂-2,8-Ph₂-1,2,8-closso-PtC₂B₉H₉的反应中不可能存在六重协同的钻石-方形-钻石机制。新化合物1,1-(PR₃)₂-2,4-Ph₂-7-OEt-closso-1,2,4-PtC₂B₉H₈(R₃=Me₂Ph 5a或Et₃ 5b)也已合成，并通过多核NMR光谱完全表征。
• Crystal and molecular structures of the nido-carborane anions, 7,9- and 2,9-C2B9H12−
  作者：Mark A. Fox、Andrés E. Goeta、Andrew K. Hughes、Andrew L. Johnson

  DOI：10.1039/b108937d

  日期：——

  Deboronation of meta-carborane, closo-1,7-C2B10H12, with refluxing piperidine results in the quantitative formation of [(C5H10NH)2H+](nido-7,9-C2B9H12−) whose structure was determined by X-ray diffraction. Heating under vacuum liberates piperidine to give (C5H10NH2+)(nido-7,9-C2B9H12−). The reaction of meta-carborane with KOH in refluxing ethanol yields K+nido-7,9-C2B9H12− and the cage substituted anion 10-EtO-7,9-C2B9H11−. The protonated Proton Sponge salt (PSH+)(nido-7,9-C2B9H12−) (PS = 1,8-N,N,N′,N′-tetramethylnaphthalenediamine) was obtained by metathesis from the potassium salt, an X-ray crystallographic study located the bridging hydrogen in the anion on the open face between the two adjacent boron atoms. Anaerobic deboronation of para-carborane, closo-1,12-C2B10H12, with KOH in refluxing tetraglyme–toluene gives the potassium salt of nido-2,9-C2B9H12− from which 2,9-C2B9H13 was isolated in 45% yield by protonation. The salt (PSH+)(nido-2,9-C2B9H12−), obtained from nido-2,9-C2B9H13 and PS, was shown by single crystal X-ray crystallography to contain a hydrogen bridging two boron atoms opposite the carbon atom on the open face. Aerobic deboronation of para-carborane with KOH forms closo-1,10-C2B8H10 and 2-HO-closo-1,10-C2B8H9 in low yields. Fully assigned multinuclear NMR (11B, 13C and 1H) data are reported for the isomeric 7,8-, 7,9- and 2,9-nido-C2B9H12− anions and neutral 7,8- and 2,9-C2B9H13, and compared with computed shifts (at the GIAO B3LYP/6-311G* level) from optimized (at MP2/6-31G*) geometries.

  meta-卡博烷（closo-1,7-C2B10H12）与回流的哌啶反应，定量生成了[(C5H10NH)2H+](nido-7,9-C2B9H12−)，其结构通过X射线衍射确定。真空加热释放哌啶，得到(C5H10NH2+)(nido-7,9-C2B9H12−)。meta-卡博烷与KOH在回流的乙醇中反应，生成K+nido-7,9-C2B9H12−和笼子取代的阴离子10-EtO-7,9-C2B9H11−。通过从钾盐的交换反应获得了质子化的质子海绵盐(PSH+)(nido-7,9-C2B9H12−)（PS = 1,8-N,N,N′,N′-四甲基萘二胺），X射线晶体学研究定位了阴离子中两个相邻硼原子之间的桥接氢。para-卡博烷（closo-1,12-C2B10H12）在回流的四甘醇-甲苯中用KOH进行厌氧去硼反应，得到nido-2,9-C2B9H12−的钾盐，并通过质子化以45%的产率分离出2,9-C2B9H13。从nido-2,9-C2B9H13和PS获得的盐(PSH+)(nido-2,9-C2B9H12−)通过单晶X射线晶体学证明包含一个桥接两个硼原子的氢，位于开放面上与碳原子相对的位置。用KOH对para-卡博烷进行有氧去硼反应，生成closo-1,10-C2B8H10和2-HO-closo-1,10-C2B8H9，产率较低。报告了同分异构体7,8-、7,9-和2,9-nido-C2B9H12−阴离子以及中性7,8-和2,9-C2B9H13的完全分配的多核NMR（11B、13C和1H）数据，并与从优化（在MP2/6-31G*下）几何结构计算的位移（在GIAO B3LYP/6-311G*水平）进行比较。
• Direct B–H Functionalization of Icosahedral Carboranes <i>via</i> Hydrogen Atom Transfer
  作者：Hongyuan Ren、Ping Zhang、Jingkai Xu、Wenli Ma、Deshuang Tu、Chang-sheng Lu、Hong Yan

  DOI：10.1021/jacs.3c01314

  日期：——

  occurs at the most electron-rich boron vertex with the lowest B–H bond dissociation energy (BDE). Using this strategy, diverse carborane derivatization, including thiolation, selenation, alkynylation, alkenylation, cyanation, and halogenation, have been achieved in satisfactory yields under a photoinitiated condition in a metal-free and redox-neutral fashion. Moreover, the synthetic utility of the current

  由于在相似的化学环境中存在 10 个惰性 B-H 键，硼顶点处二十面体碳硼烷 (C 2 B 10 H 12 ) 的高效和选择性官能化是一项长期存在的挑战。在此，我们报告了一种新的反应范式，用于通过通过以氮为中心的自由基介导的氢原子转移 (HAT) 策略实现 B-H 均裂。碳硼烷 B-H 键的 HAT 过程和由此产生的以硼为中心的碳硼烷基自由基中间体均已通过实验得到证实。该反应发生在 B-H 键解离能 (BDE) 最低的最富电子的硼顶点处。使用这种策略，在光引发条件下，以无金属和氧化还原中性的方式，已经以令人满意的产率实现了多种碳硼烷衍生化，包括硫醇化、硒化、炔基化、烯基化、氰化和卤化。此外，当前协议的合成效用也通过放大反应和基于碳硼烷的功能分子的构建得到了证明。所以，
• Cage-fluorination during deboronation of meta-carboranes
  作者：Mark A. Fox、Kenneth Wade

  DOI：10.1016/s0277-5387(96)00520-7

  日期：1997.1

  Reactions of the meta carboranes 1,7-RR'-1,7-C2B10H10 (R, R' = Me; R = Ph, R' = Me; R, R' = Ph; R, R' = 4-FC6H4) with tetrabutylammonium fluoride hydrate (TBAFH) in refluxing tetrahydrofuran gave the corresponding nido-7,9-RR'-7,9-C2B9H10- salts, The aryl carboranes and TBAFH also yielded salts of the B-fluorinated anions 10-F-7,9-RR'-7,9-C2B9H9- and 3-F-7,9-RR'-7,9-C2B9H9-. The reaction of 1,7-(4-FC6H4)(2)-1,7-C2B10H10 with TBAFH monitored by F-19 NMR showed cage fluorination occurred during deboronation to give 10-F-7,9-(4-FC6H4)(2)-7,9-C2B9H9-. The latter anion rearranged spontaneously to 3-F-7,9-(4-FC6H4)(2)-7,9-C2B9H9- under the reaction conditions. The B-11, C-13, H-1 and F-19 NMR spectra of the carboranes have been assigned. (C) 1997 Published by Elsevier Science Ltd.