Dimethylsilacalix[4]-1,3-(3',5'-diphenylphosphinine-2',6'-diyl)-2,4-(thiophene-2',5'-diyl) | 241812-08-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: Dimethylsilacalix[4]-1,3-(3',5'-diphenylphosphinine-2',6'-diyl)-2,4-(thiophene-2',5'-diyl)
• 英文别名: 2,2,7,7,13,13,18,18-Octamethyl-9,11,20,22-tetraphenyl-24,26-dithia-23,25-diphospha-2,7,13,18-tetrasilapentacyclo[17.3.1.13,6.18,12.114,17]hexacosa-1(22),3,5,8,10,12(25),14,16,19(23),20-decaene；2,2,7,7,13,13,18,18-octamethyl-9,11,20,22-tetraphenyl-24,26-dithia-23,25-diphospha-2,7,13,18-tetrasilapentacyclo[17.3.1.13,6.18,12.114,17]hexacosa-1(22),3,5,8,10,12(25),14,16,19(23),20-decaene
• CAS: 241812-08-8
• 化学式: C₅₀H₅₀P₂S₂Si₄
• 分子量: 889.369
• InChiKey: VEYOPUNHRRUNII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.24
• 重原子数：
  58
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Dimethylsilacalix[4]-1,3-(3',5'-diphenylphosphinine-2',6'-diyl)-2,4-(thiophene-2',5'-diyl) 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成
  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：

  chlorodimethyl(phenylethynyl)silane 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 195.5h， 生成 Dimethylsilacalix[4]-1,3-(3',5'-diphenylphosphinine-2',6'-diyl)-2,4-(thiophene-2',5'-diyl)
  参考文献：
  名称：

  Synthesis and X-Ray Crystal Structures of Silacalix[n]phosphinines: The First sp2-Based Phosphorus Macrocycles

  摘要：

  DOI：

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

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
• 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.