2,2,2,2-tetramethyl-2l7-propane compound with neopentane (1:1) | 126970-47-6

• 英文名称: 2,2,2,2-tetramethyl-2l7-propane compound with neopentane (1:1)
• CAS: 126970-47-6
• 化学式: F₆Sb*I₄P
• 分子量: 774.332
• InChiKey: HBTWKTYOCSDBTE-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  6.54
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  、 三碘化磷 以 一氟三氯甲烷 为溶剂， 以29%的产率得到2,2,2,2-tetramethyl-2l7-propane compound with neopentane (1:1)
  参考文献：
  名称：

  The PI4+ cation has an extremely large negative 31P nuclear magnetic resonance chemical shift, due to spin–orbit coupling: A quantum-chemical prediction and its confirmation by solid-state nuclear magnetic resonance spectroscopy

  摘要：

  We have used density-functional methods including explicit spin–orbit corrections, to calculate the 31P nuclear magnetic resonance (NMR) chemical shifts of the tetrahalophosphonium cations PX4+ (X=F, Cl, Br, I). The agreement between theory and experimental literature data for PF4+, PCl4+, and PBr4+ is good. For PI4+, the calculations predict an extremely negative (high-field) shift of approximately −520 ppm, due to particularly large spin–orbit contributions from the four heavy iodine substituents, transmitted to the phosphorus nucleus by a very effective Fermi-contact mechanism. No experimental data were available for PI4+. We have, therefore, prepared the compounds PI4AsF6, PI4SbF6, PI4AlI4, and PI4GaI4 and recorded their solid-state 31P NMR spectra, both with and without magic-angle spinning of the sample. Using the noncoordinating AsF6− and SbF6− anions, the measured isotropic shifts are −519 and −517 ppm, respectively, in good agreement with the predicted extreme value for the isolated cation. In contrast, δ31P values of only −304 and −295 ppm are found for PI4AlI4 and PI4GaI4, respectively. The large deviation from the isolated-cation limit in the latter two compounds is probably related to significant I⋯I secondary bonding interactions, as found in the solid-state structure of PI4AlI4. The observed solid-state shift tensors are discussed. The present results disagree clearly with previous claims for the synthesis of PI5.

  DOI：

  10.1063/1.478243

文献信息

• The preparation and characterization by Raman spectroscopy of Pl₄⁺AsF₆^–containing the tetraiodophosphonium cation
  作者：Inis Tornieporth-Getting、Thomas Klapötke

  DOI：10.1039/c39900000132

  日期：——

  The thermodynamically unstable PI4+AsF6- containing the first and only example of a tetrahedral PI4+4 cation, formally a derivative of the unknown PI5, was prepared by the reaction of PI3 and I3+AsF6– at low temperatures and characterized by Raman spectroscopy.

  在热力学不稳定的PI 4 + ASF 6 -含有四面体PI的第一和唯一的例子4 + 4阳离子，正式一个未知PI的衍生物5，通过PI的反应制备3和我3 + ASF 6 -在低温度和拉曼光谱表征。