1-(diphenylphosphino)-8-naphthyldimesitylborane | 1434000-95-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(diphenylphosphino)-8-naphthyldimesitylborane
• 英文别名: 2,2-Diphenyl-3,3-bis(2,4,6-trimethylphenyl)-2-phosphonia-3-boranuidatricyclo[6.3.1.04,12]dodeca-1(11),4(12),5,7,9-pentaene
• CAS: 1434000-95-9
• 化学式: C₄₀H₃₈BP
• 分子量: 560.526
• InChiKey: KIGVVIMFBJRYAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.96
• 重原子数：
  42
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(diphenylphosphino)-8-naphthyldimesitylborane 、 水 在 (二氯碘)-苯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以40%的产率得到2,2-Diphenyl-4,4-bis(2,4,6-trimethylphenyl)-3-oxa-2-phosphonia-4-boranuidatricyclo[7.3.1.05,13]trideca-1(12),5(13),6,8,10-pentaene
  参考文献：
  名称：

  Highly Congested Donor–Acceptor P–B Compound: Synthesis and Properties of a BMes₂- and a PPh₂-Functionalized 1,8-Naphthalene

  摘要：

  A PPh2- and BMes(2)-functionalized (Mes = mesityl) 1,8-naphthalene molecule (1) has been synthesized and fully characterized. Compound 1 is a highly congested molecule with a P B dative bond. NMR studies support that the P B bond in 1 is persistent in solution. Compound 1 is thermally and photochemically stable. It is highly fluxional in solution. The only reactivity it displays is its reactions with halogen molecules (PhI center dot Cl-2 and I-2), leading to the isolation of a hydrolyzed product 2, in which an oxygen atom is inserted between the P and B atom. The crystal structures of 1 and 2, have been determined by single-crystal X-ray diffraction analyses. A DFT computational study established that the open form of 1 has a P-B separation distance of 3.00 angstrom, much longer than the closed one (2.23 angstrom). Furthermore, a computational study showed that the energy difference between the two forms is very small, similar to 1 kcal/mol, which can be attributed to the highly congested nature of the molecule.

  DOI：

  10.1021/om4002846
• 作为产物：
  描述：

  1,8-二碘萘 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 1-(diphenylphosphino)-8-naphthyldimesitylborane
  参考文献：
  名称：

  Highly Congested Donor–Acceptor P–B Compound: Synthesis and Properties of a BMes₂- and a PPh₂-Functionalized 1,8-Naphthalene

  摘要：

  A PPh2- and BMes(2)-functionalized (Mes = mesityl) 1,8-naphthalene molecule (1) has been synthesized and fully characterized. Compound 1 is a highly congested molecule with a P B dative bond. NMR studies support that the P B bond in 1 is persistent in solution. Compound 1 is thermally and photochemically stable. It is highly fluxional in solution. The only reactivity it displays is its reactions with halogen molecules (PhI center dot Cl-2 and I-2), leading to the isolation of a hydrolyzed product 2, in which an oxygen atom is inserted between the P and B atom. The crystal structures of 1 and 2, have been determined by single-crystal X-ray diffraction analyses. A DFT computational study established that the open form of 1 has a P-B separation distance of 3.00 angstrom, much longer than the closed one (2.23 angstrom). Furthermore, a computational study showed that the energy difference between the two forms is very small, similar to 1 kcal/mol, which can be attributed to the highly congested nature of the molecule.

  DOI：

  10.1021/om4002846

文献信息

• <i>Peri</i>-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs
  作者：Jens Beckmann、Emanuel Hupf、Enno Lork、Stefan Mebs

  DOI：10.1021/ic401406k

  日期：2013.10.21

  The synthesis and molecular structures of 1-(diphenylphosphino)-8-naphthyldimesitylborane (1) and 5-(diphenylphosphino)-6-acenaphthyldimesitylborane (2) are reported. The experimentally determined P B pen distances of 2.162(2) and 3.050(3) angstrom allow 1 and 2 to be classified as regular and frustrated Lewis pairs. The electronic characteristics of the (non)bonding P B contacts are determined by analysis of a set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities. These densities are analyzed utilizing the atoms-in-molecules (AIM), stockholder, and electron-localizability-indicator (ELI-D) space partitioning schemes. The recently introduced mapping of the electron localizability on the ELI-D basin surfaces is also applied. All RSBIs clearly discriminate the bonding P B contact in 1 from the nonbonding P B contact in 2, which is due to the fact that the acenaphthene framework is rather rigid, whereas the naphthyl framework shows sufficient conformational flexibility, allowing shorter pen interations. The results are compared to the previously known prototypical phosphinoborane Ph3PB(C6F5)(3), which serves as a reference for a bonding P B interaction. The most prominent features of the nonbonding P B contact in 2 are the lack of an AIM bond critical point, the unaffected Hirshfeld surfaces of the P and B atomic fragments, and the negligible penetration of the electron population of the ELI-D lone pair basin of the P atom into the AIM B atomic basin.