chlorotris(dimethylamino)phosphonium iodide | 71377-24-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: chlorotris(dimethylamino)phosphonium iodide
• 英文别名: tris(dimethylamino)chlorophosphonium iodide
• CAS: 71377-24-7
• 化学式: C₆H₁₈ClN₃P*I
• 分子量: 325.56
• InChiKey: CNKXBMAEVBTUIK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.41
• 重原子数：
  12.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.72
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  chlorotris(dimethylamino)phosphonium chloride 在 碘甲烷 作用下， 反应 1.0h， 以97%的产率得到chlorotris(dimethylamino)phosphonium iodide
  参考文献：
  名称：

  Kukhar', V. P.; Pasternak, V. I.; Shevchenko, I. V., Journal of Organic Chemistry USSR (English Translation), 1981, p. 161 - 166

  摘要：

  DOI：

文献信息

• Preference for a C3 conformation in tris-dimethylaminophosphonium cations: A comparison of the reactions of (Me2N)3P with I–X (X = Cl, Br, I, CN)
  作者：Nicholas A. Barnes、Stephen M. Godfrey、Ruth T. A. Halton、Robin G. Pritchard、Zaki Safi、Joanne M. Sheffield

  DOI：10.1039/b705651f

  日期：——

  Tris-(dimethylamino)phosphine reacts with I2 to form (Me2N)3PI2, which when recrystallised from acetonitrile displays a structure of overall stoichiometry [(Me2N)3PI}I]6·CH3CN 1. The asymmetric unit of 1 consists of four different [(Me2N)3PI]+ cations, one of these exhibits a cation–anion interaction to an iodide ion, with an I–I contact distance of 3.6378(14) Å, the longest yet observed for an R3PI2 compound. Two of the other three cations display no interactions, whilst a cation–solvent interaction is observed for the fourth. When (Me2N)3PI2 is recrystallised from dichloromethane the molecule abstracts chlorine from the solvent to form [(Me2N)3PCl]I 2; this latter compound can also be synthesised directly from (Me2N)3P and ICl. The reaction of (Me2N)3P with IBr forms [(Me2N)3PBr]I, 3, which when recrystallised from chlorinated solvents forms [(Me2N)3PCl0.5Br0.5]I, 3b. The analogous [(Me2N)3PCN]I, 4 does not display CN–Cl exchange and can be recrystallised from dichloromethane. The structures of 1, 2, 3b and 4 have all been determined by X-ray diffraction. All of the (Me2N)3P groups in the cations in 1, 2, 3b and 4 exhibit a C3 conformation, in contrast to the majority of (R2N)3P systems where a Cs conformation is usually preferred. This C3 conformation appears to be favoured where there is increased positive charge on phosphorus, as is the case in the phosphorus(V) ionic species described herein. This conformation allows greater P–N π-bonding, and as a result the P–N bonds are shortened, varying between 1.566(10) and 1.624(10) Å in these compounds.

  三(二甲氨基)膦与碘（I2）反应生成（Me2N）3PI2，经过从乙腈重结晶后，显示出总体化学计量比为[(Me2N)3PI}I]6·CH3CN 1。化合物1的非对称单元包含四种不同的[(Me2N)3PI]+阳离子，其中一个显示出与碘离子之间的阳离子-阴离子相互作用，I-I接触距离为3.6378(14) Å，这是迄今为止观察到的R3PI2化合物中最长的接触距离。其余三个阳离子中的两个没有显示出相互作用，而第四个阳离子则观察到了阳离子-溶剂的相互作用。当（Me2N）3PI2在二氯甲烷中重结晶时，分子从溶剂中吸收氯，形成[(Me2N)3PCl]I 2；后者也可以直接由（Me2N）3P和ICl合成。将（Me2N）3P与IBr反应生成[(Me2N)3PBr]I 3，经过氯化溶剂重结晶后形成[(Me2N)3PCl0.5Br0.5]I 3b。类似的[(Me2N)3PCN]I 4不显示CN-Cl交换并可以从二氯甲烷中重结晶。化合物1、2、3b和4的结构均通过X射线衍射确定。在1、2、3b和4中的阳离子中，所有（Me2N）3P基团都表现出C3构象，与大多数（R2N）3P系统中通常偏好的Cs构象相对。C3构象似乎在磷的正电荷增加时更为有利，如本文中描述的磷(V)离子种所示。该构象允许更强的P-N π-键合，因此P-N键的长短各异，在这些化合物中介于1.566(10)和1.624(10) Å之间。
• Gorbatenko, Zh. K.; Mitel'man, I. E.; Feshchenko, N. G., Journal of general chemistry of the USSR, 1980, vol. 50, # 8, p. 1400 - 1403
  作者：Gorbatenko, Zh. K.、Mitel'man, I. E.、Feshchenko, N. G.

  DOI：——

  日期：——