1,1,1-tris[bis(o-tolyl)phosphanylmethyl]ethane | 197658-76-7

• 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: 1,1,1-tris[bis(o-tolyl)phosphanylmethyl]ethane
• 英文别名: [3-Bis(2-methylphenyl)phosphanyl-2-[bis(2-methylphenyl)phosphanylmethyl]-2-methylpropyl]-bis(2-methylphenyl)phosphane
• CAS: 197658-76-7
• 化学式: C₄₇H₅₁P₃
• 分子量: 708.843
• InChiKey: KKPWCKZRPPVQGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.24
• 重原子数：
  50.0
• 可旋转键数：
  12.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,1,1-tris[bis(o-tolyl)phosphanylmethyl]ethane 在 水 、 lithium 作用下， 生成 [2-methyl-3-(2-methylphenyl)phosphanyl-2-[(2-methylphenyl)phosphanylmethyl]propyl]-(2-methylphenyl)phosphane
  参考文献：
  名称：

  Diastereoselectivity in the Reaction of RCH ₂ C[CH ₂ P (Ar)(Lr)] ₃ with Electrophiles: Enhancement of Diastereoselective Control by η ³ ‐Coordination in {RCH ₂ C[CH ₂ P(Ar)(Li) ₃ }Mo(Co) ₃

  摘要：

  AbstractFollowing a procedure developed for H3CC[CH2P(Ph)2]3 (1a) as the starting compound, various tripod ligands RCH2C[CH2P(Ar)2]3 (1) have been transformed into the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 with various electrophiles R′ — Hal leads to the two diastereomers of RCH2C[CH2P‐(Ar)(R)]3 (6) with an (RRR/SSS : RRS/SSR) ratio close to the statistical value of 1:3, except when ArPh and R′Bzl, where the RRS/SSR diastereomer is obtained almost exclusively. In contrast, the reaction of [RCH2C[CH2P(Ar)(Li)[3]‐Mo(CO)3 (4) with electrophiles R′ — Hal tends to favour the formation of the homochiral RRR/SSS diastereomers. The triphosphide coordination compounds 4 are available by two different routes: either the complexes (RCH2C[CH2P‐(Ar)(H)]3Mo(CO)3, obtained from 2 and (CH3CN)3Mo(CO)3, are deprotonated by MeLi, or the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 are reacted with (CH3CN)3Mo(CO)3 to produce 4 in high yields. The ration in which the two diastereomeric forms of 5 are obtained depends on the nature of the electrophile: the greatest diastereomeric discrimination is obtained for ArPh, RPh, R′Bzl, where the homochiral relative to the RRS/SSR pair. Two‐dimensional NMR spectra and simulations of one‐dimensional spectra are used to ascertain the diastereomeric excess in each case. X‐ray analyses of three compounds of type 5 (5d, ArPh, RH, R′Ph, R′Bzl) indicate the remarkable conformational stability of the tripod metal scaffolding, with the conformations observed for these three compounds in three different solid‐state environments being closely similar, even with respect to the torsional arrangement of the phosphorus‐bound benzyl groups.

  DOI：

  10.1002/cber.19971301006
• 作为产物：
  描述：

  1,1,1-三氯甲基乙烷 、 二(邻甲苯基)膦 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 6.0h， 以62%的产率得到1,1,1-tris[bis(o-tolyl)phosphanylmethyl]ethane
  参考文献：
  名称：

  如何预测活化障碍 - 化合物 CH3C(CH2PPh2)3–n[CH2P(oTol)2]nMo(CO)3 (n = 1–3) 的构象转换：力场计算与 NMR 数据

  摘要：

  三脚架金属实体 tripodM 是空间拥挤的系统。因此，化合物 CH3C(CH2PPh2)3–n[CH2P(oTol)2]nMo(CO)3 (n = 1: 1, n = 2: 2, n = 3: 3) 所采用的构象将在很大程度上取决于排斥力作用在这些分子中。邻甲苯基的空间需求阻碍了它们的自由旋转和对映异构化过程，涉及整个化合物的速度足够慢以允许通过 NMR 技术对其进行分析。通过线形分析、EXSY 方法和聚结实验的组合，这些构象对映异构化过程的 ΔG‡ 值已确定为 ΔG‡298K = 54.3、57.9、65.5 kJ·mol–1，对于化合物 1、2 和3、分别。通过对力场产生的超曲面进行详尽搜索，计算出的活化能分别为 53、57 和 69 kJ·mol–1。因此，力场方法正确地再现了活化能对邻甲苯基取代度的依赖性。此外，力场模拟还可以深入了解对映异构化途径的各个微步骤。

  DOI：

  10.1002/(sici)1099-0682(200004)2000:4<597::aid-ejic597>3.0.co;2-7

文献信息

• Homogeneous Catalytic Hydrogenation of CO ₂ to Methanol – Improvements with Tailored Ligands
  作者：Florian Korbinian Scharnagl、Maximilian Franz Hertrich、Gordon Neitzel、Ralf Jackstell、Matthias Beller

  DOI：10.1002/adsc.201801314

  日期：——

  Improved molecularly‐defined cobalt catalysts for the hydrogenation of carbon dioxide to methanol have been developed. A key factor for increased productivity (up to twofold compared to previous state‐of‐the‐art‐system) is the specific nature of substituents on the triphos ligand. In addition, the effect of metal precursors, and variations of additives have been investigated.

  已经开发出了用于将二氧化碳加氢成甲醇的改进的分子限定的钴催化剂。生产率提高的关键因素（是三聚体配体上取代基的特殊性质）（是以前最先进的系统的两倍）。另外，已经研究了金属前体的作用以及添加剂的变化。