Dimethylsilacalix[4](3,5-diphenylphosphinine-2,6-diyl)

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Dimethylsilacalix[4](3,5-diphenylphosphinine-2,6-diyl)
• 英文别名: 2,2,8,8,14,14,20,20-Octamethyl-4,6,10,12,16,18,22,24-octakis-phenyl-25,26,27,28-tetraphospha-2,8,14,20-tetrasilapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• 化学式: C₇₆H₆₈P₄Si₄
• 分子量: 1217.61
• InChiKey: VJLYPBSVOSVCQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.95
• 重原子数：
  84
• 可旋转键数：
  8
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	2,6-Bis[dimethyl(phenylethynyl)silyl]-3,5-diphenylphosphinine	193748-78-6	C37H33PSi2	564.814

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 Dimethylsilacalix[4](3,5-diphenylphosphinine-2,6-diyl) 以 二氯甲烷 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  Formation and Structure of Rh⁽⁰⁾ Complexes of Phosphinine-Containing Macrocycles:  EPR and DFT Investigations

  摘要：

  Electrochemical and chemical reductions of Rh-(I) complexes of L-P4 (a macrocycle containing four phosphinine rings) and of L-P2S2 (a macrocycle containing two phosphinine rings and two thiophene rings) lead, in liquid solution, to EPR spectra exhibiting large hyperfine couplings with P-31 nuclei. An additional coupling (27 MHz) with Rh-103 is detected, in the liquid state, for the spectrum obtained with [LP2S2Rh(0)]; moreover, resolved P-31 hyperfine structure is observed in the frozen solution spectrum of this latter complex. DFT calculations performed on Rh-(1) complexes of model macrocycles L'(P4) and L'(P2S2) indicate that, in these systems, the metal coordination is planar and that one-electron reduction induces a small tetrahedral distortion. The calculated couplings, especially the dipolar tensors predicted for [L'Rh-P2S2((0))], are consistent with the experimental results. Although the unpaired electron is mostly delocalized on the ligands, the replacement of two phosphinines by two thiophenes tends to increase the rhodium spin density (rho(Rh) = 0.35 for [L'Rh-P2S2((0))]). It is shown that coordination to Rh as well as one-electron reduction of the resulting complex provoke appreciable changes in the geometry of the macrocycle.

  DOI：

  10.1021/jp014339z
• 作为产物：
  描述：

  双(苯基乙炔基)二甲基硅烷 以 甲苯 为溶剂， 反应 14.0h， 生成 Dimethylsilacalix[4](3,5-diphenylphosphinine-2,6-diyl)
  参考文献：
  名称：

  新的碳-磷大环化合物

  摘要：

  描述了几种基于磷和膦的大环化合物的合成。由于磷的低反转势垒，第一个是灵活的。异构体的混合物可直接用于配位化学。第二个不受构象问题的困扰，并显示出强大的 π 受体特性。

  DOI：

  10.1080/10426509908546229

文献信息

• Gold(I) and Gold(0) Complexes of Phosphinine-Based Macrocycles
  作者：Nicolas Mézailles、Narcis Avarvari、Nicole Maigrot、Louis Ricard、François Mathey、Pascal Le Floch、Laurent Cataldo、Théo Berclaz、Michel Geoffroy

  DOI：10.1002/(sici)1521-3773(19991102)38:21<3194::aid-anie3194>3.0.co;2-o

  日期：1999.11.2

  A "CO-like matrix", showing coordination analogous to that of carbonyl groups, is provided by silacalix[4]phosphinine macrocycles. Reaction with Au(I) leads to the first gold(I) complexes of macrocycles, which can be reduced with sodium or potassium to the paramagnetic gold(0) complexes (an example is shown), as evidenced by cyclic voltammetry and EPR spectroscopy.
• Synthesis and X-Ray Crystal Structures of Silacalix[n]phosphinines: The First sp2-Based Phosphorus Macrocycles
  作者：Narcis Avarvari、Nicole Maigrot、Louis Ricard、François Mathey、Pascal Le Floch

  DOI：10.1002/(sici)1521-3765(19990702)5:7<2109::aid-chem2109>3.0.co;2-q

  日期：1999.7.2
• New Carbon-Phosphorus Macrocycles
  作者：Francois Mathey、Francois Mercier、Pascal Le Floch

  DOI：10.1080/10426509908546229

  日期：1999.1.1

  The synthesis of several phosphole and phosphinine-based macrocycles is described. The first ones are flexible as a result of the low inversion barrier of phosphorus. The mixture of isomers can be directly used in coordination chemistry. The second ones are not plagued by conformational problems and display strong π-acceptor properties.

  描述了几种基于磷和膦的大环化合物的合成。由于磷的低反转势垒，第一个是灵活的。异构体的混合物可直接用于配位化学。第二个不受构象问题的困扰，并显示出强大的 π 受体特性。
• Formation and Structure of Rh⁽⁰⁾ Complexes of Phosphinine-Containing Macrocycles:  EPR and DFT Investigations
  作者：Laurent Cataldo、Sylvie Choua、Théo Berclaz、Michel Geoffroy、Nicolas Mézailles、Narcis Avarvari、François Mathey、Pascal Le Floch

  DOI：10.1021/jp014339z

  日期：2002.3.1

  Electrochemical and chemical reductions of Rh-(I) complexes of L-P4 (a macrocycle containing four phosphinine rings) and of L-P2S2 (a macrocycle containing two phosphinine rings and two thiophene rings) lead, in liquid solution, to EPR spectra exhibiting large hyperfine couplings with P-31 nuclei. An additional coupling (27 MHz) with Rh-103 is detected, in the liquid state, for the spectrum obtained with [LP2S2Rh(0)]; moreover, resolved P-31 hyperfine structure is observed in the frozen solution spectrum of this latter complex. DFT calculations performed on Rh-(1) complexes of model macrocycles L'(P4) and L'(P2S2) indicate that, in these systems, the metal coordination is planar and that one-electron reduction induces a small tetrahedral distortion. The calculated couplings, especially the dipolar tensors predicted for [L'Rh-P2S2((0))], are consistent with the experimental results. Although the unpaired electron is mostly delocalized on the ligands, the replacement of two phosphinines by two thiophenes tends to increase the rhodium spin density (rho(Rh) = 0.35 for [L'Rh-P2S2((0))]). It is shown that coordination to Rh as well as one-electron reduction of the resulting complex provoke appreciable changes in the geometry of the macrocycle.