Phosphine, [(1R,2S)-1,2-diphenyl-1,2-ethanediyl]bis[diphenyl-, rel- | 134273-44-2

• 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: Phosphine, [(1R,2S)-1,2-diphenyl-1,2-ethanediyl]bis[diphenyl-, rel-
• 英文别名: meso-1,2-diphenyl-1,2-bis-(diphenylphosphino)ethane
• CAS: 134273-44-2
• 化学式: C₃₈H₃₂P₂
• 分子量: 550.62
• InChiKey: MNAJJMQVQOTSIP-MAZIBIHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.73
• 重原子数：
  40.0
• 可旋转键数：
  9.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 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：

  Phosphine, [(1R,2S)-1,2-diphenyl-1,2-ethanediyl]bis[diphenyl-, rel- 、 molybdenum hexacarbonyl 以 二乙二醇二甲醚 为溶剂， 以75%的产率得到cis-meso-tetracarbonyl-(1,2-diphenyl-1,2-bis(diphenylphosphino)ethane)molybdenum(0)
  参考文献：
  名称：

  Bookham, Jonathan L.; McFarlane, William; Thornton-Pett, Mark, Journal of the Chemical Society, Dalton Transactions

  摘要：

  DOI：
• 作为产物：
  描述：

  二苯基乙炔 、 二苯基膦 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 Phosphine, [(1R,2S)-1,2-diphenyl-1,2-ethanediyl]bis[diphenyl-, rel- 、 (E)-1-diphenylphosphino-1,2-diphenylethylene
  参考文献：
  名称：

  立体选择性地将二苯膦加成至取代的二苯乙炔：合成，NMR和X射线晶体学研究

  摘要：

  的碱催化加成二苯基膦与上述取代diphenylethynes RC CR'（R =苯基，R'=苯基，Õ甲苯基，米甲苯基或2-联苯基; R = 米间-甲苯基，R'=  ö甲苯基或米-甲苯基）产生Ph 2 PC（R）CHR'和/或Ph 2 PCH（R）CH（R'）PPh 2。Proton，13 C，13 P和二维旋转框架Overhauser增强功能11 H NMR光谱已用于确定反应的立体化学途径和产物的立体化学。通常，受阻较大的炔烃最终进行单加成反应，最终生成膦基烯烃，其中Ph 2 P附着在碳原子上取代基最少，而顺式附着在烯烃质子上，而对于受阻较小的炔烃，首先形成反式异构体，然后进一步反应得到内消旋/赤型-二膦基烷烃。在相同条件下，双（邻甲苯基）乙炔不会与Ph 2 PH反应。确定了E-和Z -Ph 2的晶体结构P（Ph）C CHPh并显示与上述反应所隐含的应变模式一致的键间角变形。还制备了膦基

  DOI：

  10.1039/a707210d

文献信息

• Dynamic coordinative exchange in rhodium(I) complexes of chiral diphosphines bearing pendant pyridyl donor groups
  作者：Jonathan L. Bookham、Darren M. Smithies、Mark Thornton Pett

  DOI：10.1039/a908984e

  日期：——

  meso-Ph2PCH(Ph)CH(Ph)PPh2}, meso-Ph2PCH(pyr)CH(pyr)PPh2}, erythro-Ph2PCH(Ph)CH(pyr)PPh2}, rac-Ph2PCH(pyr)CH(pyr)PPh2}, threo-Ph2PCH(Ph)CH(pyr)PPh2}, and threo-Ph2PCH(Ph)CH(pym)PPh2}, [pyr = 2-pyridyl, pym = 2-pyrimidyl] reacted with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to give cationic rhodium(I) complexes [Rh(COD)L}]+ (L = diphosphine ligand), which were isolated as their PF6− salts, 1–6 respectively. In 2 and in 3 the phosphine ligand adopts a P,P′,N-coordination mode whereas 1, and 4–6 exhibit simple P,P′-coordination for the parent ligands and no evidence for N-coordination is observed. In solution 2 undergoes a fluxional process involving interchange of the coordinated and non-coordinated pyridyl environments. Variable temperature NMR studies revealed an enthalpy of activation (ΔH‡) of 64.3 kJ mol−1 and an entropy of activation (ΔS‡) of 0.005 kJ K−1 mol−1 for this process in ortho-dichlorobenzene solution. Complex 3 exhibits no similar fluxional behaviour. A single-crystal X-ray analysis of 2 revealed a nitrogen–rhodium distance of 2.369(3) Å for the coordinated pyridyl group, which is slightly longer than each of the phosphorus–rhodium distances [2.2868(7) Å and 2.3649(8) Å]. This suggests a relatively weak nitrogen–rhodium bonding interaction.

  介-Ph2PCH(Ph)CH(Ph)PPh2}、介-Ph2PCH(PYR)CH(PYR)PPh2}、赤-Ph2PCH(Ph)CH(PYR)PPh2}、rac-Ph2PCH(PYR)CH(PYR)PPh2}、threo-Ph2PCH(Ph)CH(PYR)PPh2}和threo-Ph2PCH(Ph)CH(PYM)PPh2}，[PYR = 2-吡啶基、pym = 2-嘧啶基]与[Rh(COD)Cl]2（COD = 1,5-环辛二烯）反应生成阳离子铑(I)配合物[Rh(COD)L}]+（L = 二膦配体），这些配合物分别以其 PF6 盐的形式分离出来，即 1-6。在 2 和 3 中，膦配体采用了 P、P′、N 配位模式，而 1 和 4-6 中的母配体则表现出简单的 P、P′配位，没有观察到 N 配位的迹象。在溶液中，2 经历了一个涉及配位和非配位吡啶基环境互换的流动过程。变温核磁共振研究显示，在正二氯苯溶液中，这一过程的活化焓（ΔH‡）为 64.3 kJ mol-1，活化熵（ΔS‡）为 0.005 kJ K-1 mol-1。络合物 3 没有类似的通量行为。2 的单晶 X 射线分析表明，配位吡啶基的氮铑距离为 2.369(3) Å，比磷铑距离[2.2868(7) Å 和 2.3649(8) Å]稍长。这表明氮-铑成键作用相对较弱。
• Stereoselective addition reactions of diphenylphosphine: meso- and rac-1,2-diphenyl-1,2-bis(diphenylphosphino)ethane and their Group 6 metal tetracarbonyl complexes. Crystal structures of the molybdenum derivatives
  作者：Jonathan L. Bookham、William McFarlane、Mark Thornton-Pett、Simon Jones

  DOI：10.1039/dt9900003621

  日期：——

  The addition of diphenylphosphine, PPh2H, to diphenylethyne in the presence of KOBu(t) has been followed by P-31 n.m.r. spectroscopy, and according to the reaction conditions can yield cis, (2) or trans, (3), 1,2-diphenyl(diphenylphosphino)ethene and then meso, (4), or rac, (5), 1,2-diphenyl-1,2-bis(diphenylphosphino)ethane, all of which have been isolated and characterised by elemental analysis and H-1, C-13, and P-31 n.m.r. spectroscopy. The M(CO)4 (M = Cr, Mo, or W) complexes of (4) and (5) have been prepared, and the structures of the molybdenum derivatives determined by single-crystal X-ray diffraction. In the solid state the chelate rings are puckered with one axial and one equatorial CPh group for the meso diastereomer, and two equatorial for the rac. Carbon-13 n.m.r. data suggest that the latter conformation is not fully maintained in solution.