1-diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12) | 36988-95-1

• 英文名称: 1-diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12)
• 英文别名: 1-diphenylphosphanyl-2-phenyl-1,2-dicarba-closo-dodecaborane；1-diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane；1-PPh2-2-Ph-1,2-dicarba-closo-dodecaborane(12)；2-(diphenylphosphino)-1-phenyl-ortho-carborane；1-(P(C6H5)2)-2-(C6H5)-1.2-C2B10H10；1-PPh2-2-Ph-1,2-closo-C2B10H10
• CAS: 36988-95-1
• 化学式: C₂₀H₂₅B₁₀P
• 分子量: 404.502
• InChiKey: RJEGTZBYOVDTST-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：
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• 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-diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12) 在 piperidine 作用下， 以 甲苯 为溶剂， 以51%的产率得到[7-PHPh2-8-Ph-7,8-C2B9H10]
  参考文献：
  名称：

  Nido- [7,8-C2B9H10]-阴离子对Nido-o-carboranylmonophosphines中化学稳定性，碱性和31P NMR化学位移的贡献。

  摘要：

  二十面体二碳硼烷及其缩头阴离子，1-R'-1,2-C（2）B（10）H（10）（closo）和[7-R'-7,8-C（2）B（9） ）H（10）]（-）（nido）在与笼碳原子相连的取代基的α位上产生明显影响。Closo片段具有吸电子功能，而Nido阴离子具有电子释放功能。通过（31）P NMR，磷氧化和[7-PR（2）-8-R'-7,8-C（2）B（9）H（10）]（- ）的物种。（31）P NMR化学位移依赖性与[7-PR（2）-8-R'-7,8-C（2）B（9）H（10）]的R烷基或芳基性质相关（ -）。尚未发现与Nido-carboranylmonphosphine上的R取代基的氧化性质直接相关。所述Nido-烷基碳烷基单膦的碱度最高，而最低对应于Nido-芳基碳烷基单膦。可以通过考虑簇的电子性质和R基团的性质定性地进行解释。R'的影响不太重要。通过[NBu（4）] [7-P（O）Ph（2）-8-Ph-7

  DOI：

  10.1021/ic000858p
• 作为产物：
  描述：

  1-苯基-o-蒈硼烷 、 二苯基氯化膦 在 MeLi 作用下， 以 乙醚 为溶剂， 以84%的产率得到1-diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  1-Diphenylphosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12)

  摘要：

  The two crystallographically independent molecules of the title compound, 1-[(C6H5)(2)P]-2-C6H5-1,2-C2B10H10 (C20H25B10P), in the asymmetric fraction of the unit cell are highly congruent. The conformation of the cage phenyl groups is defined by theta = 1.15 degrees and the average C1-C2 distance is 1.744 (8) Angstrom which is significantly longer than that usually found for 1,2-C2B10H10 compounds. The PPh(2) substituent is tilted away from an idealized radial position on C1 as a result of intramolecular crowding.

  DOI：

  10.1107/s0108270196009109

文献信息

• Influence of the solvent and R groups on the structure of (carboranyl)R2PI2 compounds in solution. Crystal structure of the first iodophosphonium salt incorporating the anion [7,8-nido-C2B9H10]−
  作者：Rosario Núñez、Francesc Teixidor、Raikko Kivekäs、Reijo Sillanpää、Clara Viñas

  DOI：10.1039/b716217k

  日期：——

  The influence of the electron-donor or electron-acceptor capacity of the R groups (R = iPr, Ph, Et) and the solvent on the molecular geometry in solution of adducts of carboranylphosphanes [(carboranyl)iPr2P, (carboranyl)Ph2P and (carboranyl)Et2P] with I2 in 1 : 1 ratios, has been studied in detail by 31P1H} and 11B1H} NMR spectroscopies. The more electron-accepting Ph groups make the (carboranyl)Ph2P less nucleophilic, thus stabilizing the I2 encapsulated neutral biscarboranylphosphane–diiodine adducts in solution, such as (carboranyl)Ph2P⋯I–I⋯PPh2(carboranyl), generating P⋯I–I⋯P motifs. Even in a polar solvent, such as EtOH, the arrangement is preserved. The expected basicity of these carboranylphosphanes is: (carboranyl)iPr2P > (carboranyl)Et2P > (carboranyl)Ph2P. Thus, the comparatively higher basicity of (carboranyl)Et2Pvs.(carboranyl)Ph2P facilitates a higher transfer of electron density to the I2σ*, generating the ionic species, [(carboranyl)Et2PI]+I−, even in low polar solvents, such as CH2Cl2 and toluene, with no degradation of the cluster. However, in EtOH, the formation of the anionic [7,8-nido-C2B9H10]−cluster takes place by removal of one boron atom from the closocluster. The basicity of (carboranyl)iPr2P should be the highest, superior to (carboranyl)Et2P. This is observed in the reaction of these carboranylphosphanes with I2 in EtOH. Whereas the formation of P four-coordinated molecular “spoke” charge-transfer complexes, (carboranyl)iPr2P–I–I, are suggested for (carboranyl)iPr2P in low polarity solvents, ionic species are formed in ethanolic solutions, which deboronate in a few days, faster than (carboranyl)Et2P, to yield the zwitterionic species. This is attributed to the higher basicity of (carboranyl)iPr2Pvs.(carboranyl)Et2P. The X-ray crystal structure of [7-PIiPr2-8-Ph-7,8-nido-C2B9H10], 2c, obtained from the reaction of 1-PiPr2-2-Ph-closo-1,2-closo-C2B10H10 with I2 in EtOH, confirms the formation of the zwitterion. These results prove that minor changes in the nature of the R substituents on the P atom in carboranylphosphanes, along with the solvent in which the reaction takes place, produce major alterations in the geometry of the (carboranyl)R2P–I–I species in solution, and in their possible further reactivity.

  R组（R = iPr, Ph, Et）以及溶剂对羧基氢化膦类化合物[(carboranyl)iPr2P, (carboranyl)Ph2P 和 (carboranyl)Et2P]与 I2 以 1:1 比例形成的加合物在溶液中的分子几何形状的影响，已通过 31P1H} 和 11B1H} NMR 光谱法进行了详细研究。更具电子接受能力的 Ph 取代基使得 (carboranyl)Ph2P 的亲核性降低，从而在溶液中稳定了包裹 I2 的中性双羧基氢化膦-二碘加合物，例如 (carboranyl)Ph2P⁻I–I⁻PPh2(carboranyl)，生成 P⁻I–I⁻P 结构。即使在极性溶剂（如乙醇）中，这一结构依然保持。预计这些羧基氢化膦的碱性顺序为： (carboranyl)iPr2P > (carboranyl)Et2P > (carboranyl)Ph2P。因此，相较于 (carboranyl)Ph2P，(carboranyl)Et2P 较高的碱性促进了电子密度向 I2 σ* 的转移，生成离子物种 [(carboranyl)Et2PI]+I⁻，即使在低极性溶剂如 CH2Cl2 和甲苯中，也不会导致簇的降解。然而，在乙醇中，通过去除一个硼原子，形成阴离子 [7,8-nido-C2B9H10]⁻ 簇。(carboranyl)iPr2P 的碱性应该是最高的，优于 (carboranyl)Et2P。这在这些羧基氢化膦与 I2 在乙醇中的反应中得到了验证。而在低极性溶剂中，建议 (carboranyl)iPr2P 形成四配位的分子“辐条”电荷转移复合物 (carboranyl)iPr2P–I–I，但在乙醇溶液中形成离子物种，这些物种会在几天内去硼，比 (carboranyl)Et2P 更快，生成双性离子。这归因于 (carboranyl)iPr2P 较高的碱性。通过与 I2 在乙醇中反应获得的 [7-PIiPr2-8-Ph-7,8-nido-C2B9H10]，2c 的 X 射线晶体结构确认了双性离子的形成。这些结果证明，羧基氢化膦中 P 原子上 R 替代基性质的微小变化，加上反应发生的溶剂，会对 (carboranyl)R2P–I–I 物种在溶液中的几何形状以及其可能的后续反应性产生重大影响。
• Modulation of Agostic B−H⇀Ru Bonds in <i>exo</i>-Monophosphino-7,8-Dicarba-<i>nido</i>-undecaborate Derivatives
  作者：Clara Viñas、Rosario Nuñez、Francesc Teixidor、Raikko Kivekäs、Reijo Sillanpää

  DOI：10.1021/om9509002

  日期：1996.9.3

  ligands toward Ru(II). The coordination takes place by means of the exo-cluster PPh2 group and boron atoms B(2) and B(11) through B−H⇀Ru agostic bonds. The three remaining Ru(II) positions may be occupied by two equivalent or distinct neutral ancillary ligands and one coordinating anion. The 1H NMR spectra of these complexes provide evidence for the participation of two B−H's in bonding to Ru(II). A resonance

  系列化合物[7-PPh 2 -8-R-7,8-C 2 B 9 H 10 ] -表现为对Ru（II）的三配位配体。配位是通过exo团簇PPh 2和硼原子B（2）和B（11）通过B-H⇀Ru原子键进行的。其余三个Ru（II）位置可能被两个等效或不同的中性辅助配体和一个配位阴离子占据。在1这些配合物的1 H NMR光谱提供了两个BH与Ru（II）结合的证据。接近-3 ppm的共振表明B-H⇀Ru原子键具有很大的BH贡献，而接近-15 ppm的共振表明B-H⇀Ru原子键具有较大的贡献。 Ru-H。可能会产生带有中间情况的渐进性债券的等级。这些是通过合成一系列配合物[RuX（7-PPh 2 -8-RC 2 B 9 H 10）LL']实现的，其中X = Cl或H，R = H，Me或Ph，L = PPh 3，L'= PPh 3，CO，四氢噻吩或乙醇。组合已经完成。研究表明，在8簇位置的R的性质对B-H⇀
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.12, 4.82, page 53 - 65
  作者：

  DOI：——

  日期：——
• Zakharkin, L. I.; Zhubekova, M. N.; Kazantsev, A. B., Zhurnal Obshchei Khimii, 1972, vol. 42, p. 1013 - 1017
  作者：Zakharkin, L. I.、Zhubekova, M. N.、Kazantsev, A. B.

  DOI：——

  日期：——
• 1-[Chloro(diphenylphosphino)gold(I)-<i>P</i>]-2-phenyl-1,2-dicarba-<i>closo</i>-dodecaborane(12)
  作者：M. A. McWhannell、G. M. Rosair、A. J. Welch

  DOI：10.1107/s0108270197013048

  日期：1998.1.15

  The title compound, 1-[(C6H5)(2)PAuC1]-2-(C6H5)-1,2-closo-C2B10H10 or [AuC1(C6H5)(2)P(C8H15B10)}], is the first reported derivative of 1-[(C6H5)2P]-2-(C6H5)1,2-closo-C2B10H10. The conformation of the cage phenyl group is comparable with the parent carbaborylphosphine, however, the (C6H5)(2)PAuCl substituent is less tilted from an idealized radial position on Cl due to a balance between two opposing sets of intramolecular forces. The P-Au-Cl fragment adopts the expected linear geometry.