1-diphenylphosphino-2-methyl-1,2-dicarba-closo-dodecaborane(12) | 36988-94-0

• 英文名称: 1-diphenylphosphino-2-methyl-1,2-dicarba-closo-dodecaborane(12)
• 英文别名: 1-diphenylphosphino-2-methyl-1,2-dicarba-closo-dodecaborane；1-(diphenylphosphino)-2-methyl-o-carbaborane；1-PPh2-2-Me-1,2-closo-C2B10H10；(1-(2-Me-1,2-C2B10H10))Ph2P
• CAS: 36988-94-0
• 化学式: C₁₅H₂₃B₁₀P
• 分子量: 342.431
• InChiKey: QPIRCFSBDWWJJS-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-diphenylphosphino-2-methyl-1,2-dicarba-closo-dodecaborane(12) 、 碘 以 二氯甲烷 为溶剂， 生成 [1-(2-Ma-1,2-C2B10H10)PPh2]2I2
  参考文献：
  名称：

  离散的PI-IP组装：弱相互作用对膦-二碘配合物的31P NMR光谱影响很大。

  摘要：

  DOI：

  10.1002/anie.200503007
• 作为产物：
  描述：

  1-lithio-2-methyl-o-carborane 、 二苯基氯化膦 以 苯 为溶剂， 生成 1-diphenylphosphino-2-methyl-1,2-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  Zakharkin, L. I.; Zhubekova, M. N.; Kazantsev, A. B., Zhurnal Obshchei Khimii, 1972, vol. 42, p. 1013 - 1017

  摘要：

  DOI：

文献信息

• Cyclopalladated o-carboranes. Palladium transfer from cyclopalladated N,N-dimethylbenzylamines, 1C-diphenylphosphino-o-carborane and η3-allyls in carboxylic acid solvents
  作者：Alexander D. Ryabov、Alexey V. Eliseev、Ekaterina S. Sergeyenko、Alexander V. Usatov、Leonid I. Zakharkin、Valery N. Kalinin

  DOI：10.1016/s0277-5387(00)80324-1

  日期：1989.1

  -o -carborane yielding IIa. Migration of palladium(II) is also observed from the compounds with great stability towards acetic acid, namely the [PdCl(η3-allyl)]2 dimers. No such processes except with this particular ligand were found in the case of palladium(II) allyls and other entering ligands (azobenzene, 2-phenylpyridine, α-methylstyrene). The exchange processes described clearly show that complex

  1-二苯基膦基甲基-邻-甲硼烷，o-HCB10H1OCCH2PPh2（DPMC）与Na2PdCl4（甲醇）或PdCl2（PhCN）2（苯）反应，生成“双加合物”反式[PdCl2（DPMC）2]在正丙醇中热解转化为五元PdPCCB钯环，二-μ-氯代双[（1-二苯基膦基甲基-邻碳碳烷基-B，P）钯（II）]（IIa），根据1H和31P NMR分析，它是B（3）和B（4）金属化异构体的混合物。如果在LiBr或NaI的存在下进行内部触诊，则可获得相应的溴或碘桥联的二聚体。配合物IIa也可以通过在羧酸溶剂中进行配体交换来制备。特别是，钯（II）从环钯的氯桥联的N，N-二甲基苄胺或1C-二苯基膦基-o-碳硼烷迁移，即从与C，N-五和B，P-四元Palladacycles的配合物迁移 分别制得1-二苯基膦基甲基-邻-碳硼烷，得到IIa。还观察到钯（II）从对乙酸具有很大稳定性的化合物即[PdCl（η3-烯丙基）]
• 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。
• Procedure for the degradation of 1,2-(PR2)2-1,2-dicarba-closo-dodecaborane(12) and 1-(PR2)-2-R′-1,2-dicarba-closo-dodecaborane(12)
  作者：Francesc Teixidor、Clara Viñas、M. Mar Abad、Rosario Nuñez、Raikko Kivekäs、Reijo Sillanpäa

  DOI：10.1016/0022-328x(95)05558-7

  日期：1995.11

  Monophosphines and bisphosphines bearing anionic groups derived from the 7,8-dicarba-nido-undecaborate unit, such as [7-PR2-8-Me-7,8-C2B9H10]− and [7,8-(PR2)2-7,8-C2B9H10]− (R = phenyl, ethyl, isopropyl or ethoxy), were synthesized from closo-carborane precursors 1-PR2-2-Me-1,2-C2B10H10 and 1,2-(PR2)2-1,2-C2B10H10, respectively. In general, the CcP bond in the closo species is very susceptible degradation

  带有衍生自7,8-二氨基甲酰基-未脱键单元的阴离子基团的单膦和双膦，例如[7-PR 2 -8-Me-7,8-C 2 B 9 H 10 ] -和[7,8- （PR 2）2 -7,8--C 2乙9 ħ 10 ] -（R =苯基，乙基，异丙基或乙氧基），从合成的闭合碳-carborane前体1-PR 2 -2-ME-1,2- C 2 B 10 H 10和1,2-（PR 2）2 -1,2-C 2 B 10H 10。通常，将C Ç在P键闭合碳物种是非常敏感的降解反应，产生Ç Ç P裂解和产生的[7,8-C 2乙9 ħ 10 ] 2 -阴离子。保留了良好的C降解的条件Ç P发现是甲苯与1:50碳硼烷对pipeeridine比和乙醇的碳硼烷1:10至哌啶比率。所述芳基膦保持Ç Ç P键最好与产生最高的产率。亚磷酸盐还保留了C cP键，但磷变成正离子并产生两性离子物质。烷基膦是中间的，取决于-PR
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.12, 4.82, page 53 - 65
  作者：

  DOI：——

  日期：——
• Kalinin, V. N.; Usatov, A. V.; Antonovich, V. A., Journal of general chemistry of the USSR, 1988, vol. 58, p. 1621 - 1630
  作者：Kalinin, V. N.、Usatov, A. V.、Antonovich, V. A.、Zakharkin, L. I.

  DOI：——

  日期：——