1-indenyl-1,2-carborane | 889455-32-7

• 英文名称: 1-indenyl-1,2-carborane
• 英文别名: 1-(o-carboranyl)indene
• CAS: 889455-32-7
• 化学式: C₁₁H₁₈B₁₀
• 分子量: 258.374
• InChiKey: SSRKEZWRPVRTJR-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-indenyl-1,2-carborane 、 三甲胺 以 甲醇 、 水 为溶剂， 以99%的产率得到[Me3NH][(C9H7)C2B9H11]
  参考文献：
  名称：

  1-茚基-1,2-碳环烷衍生的第4组金属配合物的合成，结构表征和反应活性

  摘要：

  用1个当量M（NME的1-茚基-1,2-碳硼烷的治疗2）4的甲苯溶液（M =锆，铪），得到[η 5 - （C 2乙10 ħ 11）C 9 H ^ 6 ] M（ NME 2）3（2），将其转化为[η 5 - （C 9 H ^ 7）C 2乙9 ħ 10 ] M（NME 2）2（HNME 2）（3中HNME的存在下）2。配合物3还由[Me 3 NH] [7-C 9 H 7 -7,8-C 2 B 9 H 11 ]（4）与M（NMe 2）4等摩尔反应制备。溶解2或3 [：ησ在导致结构独特的复合物的分离的极性溶剂5 - （C 9 H ^ 6）C 2乙9 ħ 10 ] M（NME 2）（L）Ñ（M =的Ti，L = DME，n = 1（5a）； M = Zr，L = DME，n = 1（在图5b）中，L ＝ Py，n＝ 2（5b′），L ＝ THF，n＝ 2（5b′′））。的相互作用3 1或2个二异丙

  DOI：

  10.1021/om701108v
• 作为产物：
  描述：

  1-(o-carboranyl)-2-indanol 在 triphenylphosphine 、 imidazole 、 iodine 作用下， 以 甲苯 为溶剂， 以78%的产率得到1-indenyl-1,2-carborane
  参考文献：
  名称：

  Synthesis and Structural Characterization of New Carboranyl-Indenyl Ligands and Their Lanthanide Complexes

  摘要：

  Two new directly attached carboranyl-indenyl compounds, 2-(o-carboranyl)indene (2) and 1-(o-carboranyl)indene (4), were synthesized, and their applications in lanthanide chemistry were explored. Reactions of 2-indanone or indene epoxide with Li2C2B10H10 followed by dehydration reactions gave 2 or 4, respectively. Treatment of 2 with excess sodium metal afforded presumably {eta(5):eta(6)-(2-C9H6)(C2B10H11)}{Na-3(THF)(n)}, which reacted with LnCl(3) to produce dinuclear complexes [eta(5):eta(6)-(2-C9H6)(C2B10H11)Ln(THF)}(2)(mu-Cl)][Na(THF)(6)] (Ln = Y (5a), Er (5b)). Compound 4 reacted with excess sodium metal, yielding [{eta(5):eta(6)-(1-C9H6)(C2B10H11)}Na-3(THF)(5)}](2) (6), bearing a six-membered C2B4 open face and a five-membered C-5 bonding face. Reaction of 6 with LnCl(3) or Ln(BH4)(3)(THF)(3) gave [eta(5):eta(6)-(1-C9H6)(C2B10H11)Ln(THF)}(2)(mu-Cl)][Na(THF)(3)] (Ln = Y (7a), Nd (7b), Er (7c)) or {[eta(5):eta(6)-(1-C9H6)-(C2B10H11)Er(THF)](2)(mu-BH4)}{Na(THF)(2)} (8), respectively. Interaction of 8 with excess sodium metal generated {[eta(5):eta(7)-(1-C9H6)(C2B10H11)Er(THF)](2)} Na-4(THF)(8)} (9). These new complexes were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 1-4, 5b, 6, 7a, 7c, 8, and 9 were confirmed by single-crystal X-ray analyses. The results showed that these new ligands favored the formation of the "metal-bridged" type of dinuclear complexes due to the lack of the linkage between the indenyl and carboranyl units.

  DOI：

  10.1021/om0601955

文献信息

• Synthesis, structure and reactivity of highly constrained-geometry yttracarborane alkyl [ σ:η 5 -(C 9 H 6 )C 2 B 9 H 10 ]Y[ η 2 -(CH 3 OCH 2 CH 2 OCH 3 )] 2
  作者：Jingying Yang、Hao Shen、Zuowei Xie

  DOI：10.1016/j.jorganchem.2015.05.010

  日期：2015.12

  Y(CH2C6H4-o-NMe2)3 in DME (DME=1,2-dimethoxyethane) gave highly constrained-geometry yttracarborane alkyl [σ:η5-(C9H6)C2B9H10]Y(DME)2 (1) in 82% yield. Reaction of 1 with 1equiv of 2-benzoylpyridine, diphenylketone, di(2-pyridyl)ketone or diphenylketene afforded the corresponding Y–C bond insertion products [σ:η5-OC(Py) (Ph)C9H6}C2B9H10]Y(THF)2 (2), [σ:η5-OC(R2)C9H6}C2B9H10]Y(THF)3 (R=Ph (3), Py (4)) or

  制备了在配体中没有任何附加的供体官能团的稀土金属碳硼烷烷基，并首次对其进行了结构表征。在DME（DME = 1,2- ）中用1当量的Y（CH 2 C 6 H 4 - o -NMe 2）3处理[7-茚基-7,8 -C 2 B 9 H 11 ] [Me 3 NH]二甲氧基乙烷），得到高度限制几何构型yttracarborane烷基[ σ：η 5 - （C 9 H ^ 6）C 2乙9 ħ 10 ] Y（DME）2（1），产率为82％。的反应1与2-苯甲酰基，二苯甲酮，二（2-吡啶基）酮或二苯基乙烯酮，得到相应的Y-C键插入产品1equiv [ σ：η 5 - OC（PY）（PH）C 9 H ^ 6 }℃ 2乙9 ħ 10 ] Y（THF）2（2），[ σ：η 5 - OC（R 2）C 9 H ^ 6 }℃ 2乙9 ħ 10 ] Y（THF）3（R = Ph（上3），Py（4））或[σ：η 5
• Reactivity of Traditional Metal–Carbon (Alkyl) versus Nontraditional Metal–Carbon (Cage) Bonds in Organo-Rare-Earth Metal Complexes [η⁵:σ-(C₉H₆)(C₂B₁₀H₁₀)]Ln(CH₂C₆H₄-<i>o</i>-NMe₂)(THF)₂
  作者：Jingying Yang、Zuowei Xie

  DOI：10.1021/om501212e

  日期：2015.6.8

  Equimolar reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3) in THF gave highly constrained-geometry complexes [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(THF)(2) (Ln = Y (1a), Gd (1b), Dy (1c)). They reacted with RN=C=NR or 2,6-Me2C6H3NCS to generate the Ln-C-alkyl insertion products [eta(5):sigma-(C9H6)C2B10H10]Ln-(eta(2)(RN)(2)C(CH2C6H4-o-NMe2)](THF) (R = TMS, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (3a)) or [eta(5):sigma-(C9H6)C2B10H10]Dy[eta(2)-(2,6-Me2C6H3)NC(CH2C6H4-o-NMe2)S](THF)(2) (4c). Treatment of 2a with I equiv of R'N=C=NR' to give the Y-C-cage insertion complexes [eta(5):sigma-(C9H6)N(R')C(=NR')}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (R' = Cy (5a), Pr-i (6a)). Similarly, unsaturated compounds Ph2C=C=O and PY2C=O (Py = 2-pyridyl) also inserted into the Y-C-cage bond in 2a to yield [eta(5):sigma-(C9H6)OC(=CPh2)}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (7a) and [eta(5):sigma-(C9H6)OC(Py)(2)}C2B10H10]Y[eta(2)-(TMS)N)}(2)C(CH2C6H4-o-NMe2)](THF) (8a), respectively. In sharp contrast to the earlier reports that the nontraditional metal-C-cage sigma bonds in metal carboranyl complexes are generally inert toward electrophiles, the insertion of unsaturated molecules into the Y-C-cage sigma bond in 2a represents the first example of this type of reactions. These results shed some light on how to activate the nontraditional metal-carbon (cage) bonds in metal-Carboranyl complexes. All new complexes were characterized by spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.
• Synthesis and Structural Characterization of Constrained-Geometry Organolanthanide Chlorides and Alkyls Incorporating the Ligand [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]²⁻
  作者：Hao Shen、Hoi-Shan Chan、Zuowei Xie

  DOI：10.1021/om8006344

  日期：2008.10.27

  Interaction of 1-indenyl-1,2-carborane (1) with 2 equiv of KH in refluxing THF gave the dipotassium salt [K-2][(C9H6)C2B10H10]. Treatment of [K-2][(C9H6)C2B10H10] with 1 equiv of LnCl(3) in THF generated the ionic complex [K(THF)(6)][eta(5):sigma-(C9H6)C2B10H10}(2)La(THF)] (2) for early lanthanide or organolanthanide chloride complexes [eta(5):sigma-(C9H6)C2B10H10}Ln(THF)(2)(mu-Cl)(2)K(THF)(2)](2) (Ln = Y (3a), Gd (3b), Er (3c), Yb (3d)) for late lanthanides. Reaction of 3 with nucleophile NaCp or KCH2C6H4-o-NMe2 afforded the corresponding salt metathesis products [eta 5:sigma-(C9H6)C2B10H10]Ln(eta(5)-C5H5)(THF)(2) (Ln = Y (4a), Gd (4b)) or [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(DME) (Ln = Y (5a), Er (5c)), respectively. Complexes 5 were also synthesized via the alkane elimination reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3). They represent the first examples of organolanthanide alkyl complexes incorporating a carboranyl ligand. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.