(o-lithiophenyl)diisopropylphosphine | 500022-69-5

• 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: (o-lithiophenyl)diisopropylphosphine
• 英文别名: o-lithium diisopropylphenylphosphine；(o-(i-Pr)2PC6H4)Li；LiC6H4PiPr2
• CAS: 500022-69-5
• 化学式: C₁₂H₁₈LiP
• 分子量: 200.19
• InChiKey: ISNRORPNAGCNBZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (o-lithiophenyl)diisopropylphosphine 在 三乙胺 作用下， 以 四氢呋喃 、 氘代氯仿 、 二氯甲烷 为溶剂， 反应 4.83h， 生成 chloro-(η³-2-propen-1-yl)-(1,3-diisopropyl-2-(2-(diisopropylphosphino)phenyl)-5-methyl-6-oxo-6H-pyrimidinium-4-olate) palladium(II)
  参考文献：
  名称：

  Tailoring Buchwald-Type Phosphines with Pyrimidinium Betaines as Versatile Aryl Group Surrogates

  摘要：

  A derivatization of dialkylbiarylphosphines consisting in the formal replacement of their distal aryl group by a pyrimidinium betaine is reported. Two achiral representatives of this new class of Buchwald-type phosphines have been successfully synthesized through two strategies. The first one is based on a last stage introduction of the phosphino moiety, and the second one consists in a modular, one-pot, three-step procedure starting from an o-bromoaryl phosphine. The resulting phosphines have been coordinated onto gold(I) and palladium(II) centers and have been employed as supporting ligands in Pd-catalyzed SuzukiMiyaura cross-coupling of aryl halide substrates.

  DOI：

  10.1021/om5007819
• 作为产物：
  描述：

  (2-bromophenyl)diisopropylphosphine 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 以95%的产率得到(o-lithiophenyl)diisopropylphosphine
  参考文献：
  名称：

  膦酰基没食子烷的金（I）配合物：从互变到可分离的配位异构体。

  摘要：

  盖仑交换：膦酰基加仑配体与AuCl配位后，中性和两性离子复合物共存。NMR光谱学提供了直接证据，证明二膦酰基加仑中氯在金和镓之间的转移。引入第三个膦烷基支链可实现两种配位异构体的分离和结构表征（参见图片；金黄色，P红色，Cl绿色，Ga蓝色）。

  DOI：

  10.1002/anie.200900737

文献信息

• Hypervalent Silicon Compounds by Coordination of Diphosphine-Silanes to Gold
  作者：Pauline Gualco、Maxime Mercy、Sonia Ladeira、Yannick Coppel、Laurent Maron、Abderrahmane Amgoune、Didier Bourissou

  DOI：10.1002/chem.201001281

  日期：2010.9.17

  the silane as a σ‐acceptor ligand, provided it is positioned trans to gold. The nature of the second substituent at silicon (R=F, Ph, Me) has very little influence on the magnitude of the Au→Si interaction, in marked contrast to N→Si adducts. According to variable‐temperature and 2D EXSY NMR experiments, the apical/equatorial positions around silicon exchange in the slow regime of the NMR timescale

  两性二膦-硅烷配体[ o-（i Pr 2 P）C 6 H 4 ] 2 Si（R）F（R = F，Ph，Me）与AuCl的配位提供五配位中性硅化合物，其中金属原子充当刘易斯基地。X射线衍射分析，NMR光谱和DFT计算证实了这些络合物中Au→Si相互作用的存在，从而导致硅周围呈三角双锥体的几何形状。单个吸电子氟原子的存在足以观察硅烷作为σ受体配体的配位，前提是该硅烷以反式定位黄金。与N→Si加合物形成鲜明对比的是，硅上第二个取代基的性质（R = F，Ph，Me）对Au→Si相互作用的大小影响很小。根据变温和2D EXSY NMR实验，在NMR时标的慢速过程中，硅交换周围的顶/赤道位置。通过光谱表征了氟原子处于金的反式或顺式位置的两种形式，并估计了它们相互转化的活化势垒。通过DFT计算评估了两个同分异构结构的键合和相对稳定性。
• <i>ortho</i>-Phenylene-bridged phosphorus/silicon Lewis pairs
  作者：Lucas Wickemeyer、Jan Schwabedissen、Pia C. Trapp、Beate Neumann、Hans-Georg Stammler、Norbert W. Mitzel

  DOI：10.1039/d2dt04097b

  日期：——

  A series of five ortho-phenylene-bridged phosphorus–silicon Lewis pairs was synthesized, with phosphorus bearing isopropyl groups while the substituents at the silicon atom vary (–CH3, –Cl, –F). Possible interactions between Lewis acid and base were investigated both experimentally (NMR, XRD) and theoretically to determine the influence of the different substituents. Calculated ortho-interaction energies

  合成了一系列五个邻亚苯基桥接的磷-硅路易斯对，磷带有异丙基，而硅原子上的取代基不同（-CH 3、-Cl、-F）。通过实验（NMR、XRD）和理论上研究了路易斯酸和碱之间可能的相互作用，以确定不同取代基的影响。计算的邻位相互作用能 (OIE) 显示酸性和碱性单元之间的稳定相互作用，这也存在于元-和对位-相互作用能（分别为 MIE 和 PIE），表明稳定不是由直接的酸碱相互作用引起的，而是由通过环的电子相互作用引起的。进一步的光谱（NMR、XRD）和理论（NBO、QTAIM、SAPT）研究证实硅和磷之间不存在直接相互作用。
• Activation of M–Cl Bonds with Phosphine–Alanes: Preparation and Characterization of Zwitterionic Gold and Copper Complexes
  作者：Marie Sircoglou、Nathalie Saffon、Karinne Miqueu、Ghenwa Bouhadir、Didier Bourissou

  DOI：10.1021/om4005884

  日期：2013.11.25

  The triphosphine-alane [iPr(2)P(o-C6H4)](3)Al nylphosphine with AlCl3. Reactions of 1 with gold and copper (1) was prepared by coupling ortho-lithiated diisopropylphenylphosphine with AlCl3. Reactions of 1 with gold and copper chlorides afforded the zwitterionic cage complexes 2 and 3. The three phosphine arms coordinate symmetrically to the coinage metal, while the aluminum center abstracts the chloride. Coordination of the related diphosphine-alane [iPr(2)P(o-C6H4)](2)AlCl (4) to CuCl is also accompanied by a shift of the chloride atom from copper to aluminum. However, the ensuing highly electrophilic Cu+ center engages in weak intraand intermolecular Cl -> Cu interactions, resulting in the original polymeric complex S. The structures of all complexes have been ascertained spectroscopically and crystallographically, and their bonding situations have been analyzed by DFT calculations.
• Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ-Acceptor Ligands
  作者：Pauline Gualco、Tzu-Pin Lin、Marie Sircoglou、Maxime Mercy、Sonia Ladeira、Ghenwa Bouhadir、Lisa M. Pérez、Abderrahmane Amgoune、Laurent Maron、François P. Gabbaï、Didier Bourissou

  DOI：10.1002/anie.200905391

  日期：2009.12.21
• Original Transition Metal→Indium Interactions upon Coordination of a Triphosphine−Indane
  作者：Eric J. Derrah、Marie Sircoglou、Maxime Mercy、Sonia Ladeira、Ghenwa Bouhadir、Karinne Miqueu、Laurent Maron、Didier Bourissou

  DOI：10.1021/om1011769

  日期：2011.2.28

  The triphosphine-indane TPI([o-i-Pr2P(C6H4)](3)In) has been prepared and found to react with [Pd(P-t-Bu-3)(2)] and [AuCl(SMe2)]. According to X-ray diffraction analyses and DFT calculations, the ensuing complexes both display original donor acceptor M In interactions, although of markedly different nature and magnitude.