[DmpPPMe3] | 212079-67-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [DmpPPMe3]
• 英文别名: [(2,6-Mes2C6H3)PPMe3]；[2,6-Bis(2,4,6-trimethylphenyl)phenyl]phosphanylidene-trimethyl-lambda5-phosphane；[2,6-bis(2,4,6-trimethylphenyl)phenyl]phosphanylidene-trimethyl-λ5-phosphane
• CAS: 212079-67-9
• 化学式: C₂₇H₃₄P₂
• 分子量: 420.514
• InChiKey: YPFUOINFMARQQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  [DmpPPMe3] 在 水 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到2,6-dimesitylphenylphosphinic acid
  参考文献：
  名称：

  Crystal structure of the phosphanylidene-σ4-phosphorane DmpPPMe3 (Dmp=2,6-Mes2C6H3) and reactions with electrophiles

  摘要：

  The stable phosphanylidene-sigma(4)-phosphorane DmpP=PMe3 (1, Dmp = 2,6-Mes(2)C(6)H(3)) has been examined by single-crystal X-ray diffraction methods. The structure of 1 features a relatively short P-P bond length of 2.084(2) Angstrom. Reactions of 1 with various electrophiles demonstrate the nucleophilic behavior of the phosphanylidene atom of 1 and also provide access to new organophosphorus compounds. For example, addition of excess BH3 (in the form of either BH3. THF or BH3. SMe2 to 1 leads to formation of a mono-borane adduct DmpP(BH3)PMe3. Reactions of carbon and silicon based electrophiles EX (E = R3C or R3Si; X = halide or OTf-) produce either diphosphanium salts [DmpP(E)PMe3]X or phosphines DmpP(E)X. In some cases equilibrium mixtures of both product types are observed, and the equilibria can be shifted by addition of either X- or PMe3. Compound 1 is also readily protonated by HOTf, HCl and PhOH. As found for the carbon and silicon based electrophiles, the nature of the resulting product depends on the counterion. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00284-9
• 作为产物：
  描述：

  1,3-二氯苯 在 盐酸 、 正丁基锂 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 苯 为溶剂， 反应 28.33h， 生成 [DmpPPMe3]
  参考文献：
  名称：

  膦-威蒂格试剂对NHC和NHO的反应活性

  摘要：

  Phospha–Wittig试剂RPPMe 3（R = Mes * 2,4,6- t Bu 3 -C 6 H 2；Mes Ter 2,6-（2,4,6-Me 3 C 6 H 2）-C 6 H 3；Dip Ter 2,6-（2,6-iPr 2 C 6 H 3）-C 6 H 3），可以被认为是膦稳定的次膦酸酯。在这项研究中，我们表明PMe 3可以被NHC或NHO取代。有趣的是，类似次膦的反应性会导致随后的C（sp 2）– NHOs中环外CH 2基团的H活化。该概念进一步扩展到烯丙基加成的NHO，产生了膦取代的烯丙基。

  DOI：

  10.1039/d1dt00071c

文献信息

• Isolable Phospha- and Arsaalumenes
  作者：Malte Fischer、Samuel Nees、Thomas Kupfer、James T. Goettel、Holger Braunschweig、Christian Hering-Junghans

  DOI：10.1021/jacs.1c00204

  日期：2021.3.24

  DipTerPnPMe3 (Pn = P, As), so-called pnicta-Wittig reagents, at 80 °C cleanly gives the pnictaalumenes DipTerPnAlCp* with polarized Pn–Al double bonds and intramolecular stabilization through interactions of Al with a flanking aryl group of the terphenyl substituent on Pn. In contrast, using MesTerPPMe3, the reaction with 2 equiv of :AlCp3t or :AlCp* afforded the three-membered 2π-aromatic ring systems

  （AlCp *）4（在高温下为单体：AlCp *的来源）与Dip TerPnPMe 3（Pn = P，As）（所谓的pnicta-Wittig试剂）的组合在80°C时干净地得到了pnictaalumenes Dip TerPnAlCp *具有极化的Pn–Al双键和通过Al与Pn上三联苯取代基的侧基芳基相互作用而实现的分子内稳定作用。相反，使用Mes TerPPMe 3，与2当量的：AlCp 3t或：AlCp *反应，得到三元2π-芳族环系统Mes TerP（AlCp x）2（x = 3t，*）。
• ‘Phospha-Wittig’ reactions using isolable phosphoranylidenephosphines ArPPR3 (Ar = 2,6-Mes2C6H3 or 2,4,6-But3C6H2)
  作者：Shashin Shah、John D. Protasiewicz

  DOI：10.1039/a802722f

  日期：——

  Phosphoranylidenephosphines DmpPPMe3 (1a, Dmp = 2,6-Mes2C6H3) and Mes*PPMe3 (1b, Mes* = 2,4,6-But3C6H2) act as ‘Phospha-Wittig’ reagents with aldehydes providing phosphaalkenes [ArPC(H)R] in high yields.

  亚磷酰基膦 DmpPPMe3（1a，Dmp = 2,6-Mes2C6H3）和 Mes*PPMe3 （1b，Mes* = 2,4,6-But3C6H2）可作为 "磷-维蒂希 "试剂与醛类反应，以高产率提供膦烯烃 [ArPC(H)R]。
• Titanocene pnictinidene complexes
  作者：Malte Fischer、Fabian Reiß、Christian Hering-Junghans

  DOI：10.1039/d1cc01305j

  日期：——

  The phospha–Wittig reagent MesTerPPMe3 (MesTer = 2,6-2,4,6-Me3–C6H2}–C6H3) and arsa–Wittig reagent DipTerAsPMe3 (DipTer = 2,6-2,6-iPr2-C6H3}–C6H3) have been employed to synthesize the titanocene complexes Cp2Ti(PMe3)PnAr (Pn = P, As) with terminal phosphinidene or arsinidene ligands, respectively. Ab initio studies show that the description as singlet biradicaloids in their ground state is warranted

  phospha –Wittig试剂Mes TerPPMe 3（Mes Ter = 2,6- 2,4,6-Me 3 –C 6 H 2 } –C 6 H 3）和arsa–Wittig试剂Dip TerAsPMe 3（Dip Ter = 2 （6- 2,6-iPr 2 -C 6 H 3 } –C 6 H 3）已被用来合成带有末端膦亚基或亚砷基的钛茂金属配合物Cp 2 Ti（PMe 3）PnAr（Pn = P，As）配体。从头算 研究表明，将其描述为处于基态的单线态双基自由基是有道理的。
• Cycloaddition of phosphanylidene-σ⁴-phosphoranes ArPPMe₃and quinones to yield 1,3,2-dioxophospholanes
  作者：Xufang Chen、Rhett C. Smith、John D. Protasiewicz

  DOI：10.1039/b309165a

  日期：——

  The reaction of phosphanylidene-σ4-phosphoranes ArPPMe3 (Ar = 2,6-Mes2C6H3 or 2,4,6-t-Bu3C6H2) with select ortho-quinones yields 1,3,2-dioxophospholanes, one of which shows interesting π-stacking of the aromatic groups in the solid state.

  亚膦酰-Ï4-磷烷 ArPPMe3（Ar = 2,6-Mes2C6H3 或 2,4,6-t-Bu3C6H2）与精选的正醌反应生成 1,3,2-二氧磷烷，其中一种在固态下显示出有趣的芳香基团Ï-堆叠。
• A cyclic diphosphinite by a formal [4+4] cycloaddition reaction of β-phosphaenone
  作者：Xufang Chen、Weizhong Chen、Tong Ren、John D. Protasiewicz

  DOI：10.1016/j.tetlet.2005.06.131

  日期：2005.8

  Unstable β-phosphaenones formed by reaction of the phosphanylidene-σ4-phosphorane DmpP = PMe3 (Dmp = 2,6-dimesitylphenyl) with acenaphthenequinone dimerize in hexane by a formal [4+4] cycloaddition reaction to form a cyclic diphosphinite. X-ray crystallographic analysis and variable temperature 1H NMR spectra of the cyclic diphosphinite are presented.

  由phosphanylidene-σ的反应形成不稳定的β-phosphaenones 4 -phosphorane DMPP = PME 3（DMP = 2,6- dimesitylphenyl）与二聚化苊醌在己烷中的正式[4 + 4]环加成反应以形成环状diphosphinite。给出了环二亚膦酸酯的X射线晶体学分析和可变温度1 H NMR光谱。