bis(2-(di-tert-butylphosphino)ethyl) ether | 119863-03-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: bis(2-(di-tert-butylphosphino)ethyl) ether
• 英文别名: POP-t-Bu；Ditert-butyl-[2-(2-ditert-butylphosphanylethoxy)ethyl]phosphane
• CAS: 119863-03-5
• 化学式: C₂₀H₄₄OP₂
• 分子量: 362.516
• InChiKey: BJWVTYKHIBVGKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dichloro(p-cymene)ruthenium(II) dimer 、 bis(2-(di-tert-butylphosphino)ethyl) ether 以 甲苯 为溶剂， 以72%的产率得到dichloro(bis(2-(di-tert-butylphosphino)ethyl) ether)ruthenium
  参考文献：
  名称：

  Substituents Effects in POP Pincer Complexes of Ruthenium

  摘要：

  Reactions of [RuCl2(p-cymene)](2) with ((Bu2PCH2CH2)-Bu-t)(2)O (POP-Bu-t) and (Pr2PCH2CH2)(2)O (POP-Pr-i) afforded RuCl2(POP-Bu-t) (1) and [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)]Cl (2 center dot Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a gamma-agostic C-H center dot center dot center dot Ru interaction of one Bu-t group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N-2)Cl(POP-Bu-t)]BPh4 (4), which also showed agostic bonding of a Bu-t group, was obtained by substitution of N-2 for Cl- in 1, in the presence of NaBPh4. Compound 2 center dot Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2 center dot BPh4 or 2 center dot PF6 salts, respectively. A crystallographic analysis of 2 center dot PF6 established a co-facial bioctahedral geometry of the [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)](+) cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H-2 afforded the dihydrogen complexes cis,trans-Ru(H-2)Cl-2(POP-Bu-t) (3) and cis,cis-Ru(H-2)Cl-2(POP-Pr-i) (5), respectively. The H-H bond distances are very similar in both compounds, r(H-H) = 1.0 +/- 0.1 angstrom, based on the T-1min and J(HD) data and results of DFT calculations. Reaction of 2 with N-2 gave the dinitrogen complex cis,cis-Ru(N-2)Cl-2(POP-Pr-i) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-Bu-t and POP-iPr complexes 1-6.

  DOI：

  10.1021/om050053v
• 作为产物：
  描述：

  二叔丁基氯化膦 在 lithium aluminium tetrahydride 、 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.0h， 生成 bis(2-(di-tert-butylphosphino)ethyl) ether
  参考文献：
  名称：

  铑（I）的α，ω-双（二叔丁基膦基）烷烃和α，ω-双（二叔丁基膦基）（聚）醚配合物中的较不常见的配位方式†

  摘要：

  α，ω二（二-叔-butylphosphino）烷烃和α，ω -双（二-叔-butylphosphino）（聚）醚配体在可观的产量通过合适的二卤化物的反应制备具有唇形两个当量吨-卜2。[Rh（COD）（丙酮）2 ] [OTf]与先前的配体反应生成[Rh（COD）（OTf）] 2 [μ- t -Bu 2 P（CH 2）n，P -吨-Bu 2 ]（ñ = 5和8），含有协调三氟甲磺酸酯。与配体t -Bu 2 PCH 2 CH分离出2 OCH 2 CH 2 P- t -Bu 2单体配合物[Rh（COD）（P∩P）] [OTf]，其中二膦配体通过氧和一个磷原子配位。在配体t -Bu 2 P（CH 2 CH 2 O）2 CH 2 CH 2 P- t -Bu 2的情况下，桥联配合物[[Rh 2（COD）2（OTf）]（μ-P∩ P）] [OTf]形成，同时包含配位和不配位的三氟甲磺酸盐。在解决方案中，此复数重新排列为[[Rh（COD）]

  DOI：

  10.1002/recl.19881070327

文献信息

• Less common modes of coordination in α,ω-bis(di-tert-butylphosphino)alkane and α,ω-bis(di-tert-butylphosphino) (poly)ether complexes of rhodium(I)
  作者：Klaas Timmer、D. Harry M. W. Thewissen、Jan W. Marsman

  DOI：10.1002/recl.19881070327

  日期：——

  α,ω-Bis(di-tert-butylphosphino)alkane and α,ω-bis(di-tert-butylphosphino) (poly)ether ligands are prepared in appreciable yields via reaction of the appropriate dihalide with two equivalents of Lip-t-Bu2. Reaction of [Rh(COD)(acetone)2][OTf] with the former ligands yields bridged complexes of the type [Rh(COD)(OTf)]2[μ-t-Bu2P(CH2)n,P-t-Bu2] (n = 5 and 8), containing coordinated triflate. With the ligand

  α，ω二（二-叔-butylphosphino）烷烃和α，ω -双（二-叔-butylphosphino）（聚）醚配体在可观的产量通过合适的二卤化物的反应制备具有唇形两个当量吨-卜2。[Rh（COD）（丙酮）2 ] [OTf]与先前的配体反应生成[Rh（COD）（OTf）] 2 [μ- t -Bu 2 P（CH 2）n，P -吨-Bu 2 ]（ñ = 5和8），含有协调三氟甲磺酸酯。与配体t -Bu 2 PCH 2 CH分离出2 OCH 2 CH 2 P- t -Bu 2单体配合物[Rh（COD）（P∩P）] [OTf]，其中二膦配体通过氧和一个磷原子配位。在配体t -Bu 2 P（CH 2 CH 2 O）2 CH 2 CH 2 P- t -Bu 2的情况下，桥联配合物[[Rh 2（COD）2（OTf）]（μ-P∩ P）] [OTf]形成，同时包含配位和不配位的三氟甲磺酸盐。在解决方案中，此复数重新排列为[[Rh（COD）]
• Substituents Effects in POP Pincer Complexes of Ruthenium
  作者：Quinn Major、Alan J. Lough、Dmitry G. Gusev

  DOI：10.1021/om050053v

  日期：2005.5.1

  Reactions of [RuCl2(p-cymene)](2) with ((Bu2PCH2CH2)-Bu-t)(2)O (POP-Bu-t) and (Pr2PCH2CH2)(2)O (POP-Pr-i) afforded RuCl2(POP-Bu-t) (1) and [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)]Cl (2 center dot Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a gamma-agostic C-H center dot center dot center dot Ru interaction of one Bu-t group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N-2)Cl(POP-Bu-t)]BPh4 (4), which also showed agostic bonding of a Bu-t group, was obtained by substitution of N-2 for Cl- in 1, in the presence of NaBPh4. Compound 2 center dot Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2 center dot BPh4 or 2 center dot PF6 salts, respectively. A crystallographic analysis of 2 center dot PF6 established a co-facial bioctahedral geometry of the [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)](+) cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H-2 afforded the dihydrogen complexes cis,trans-Ru(H-2)Cl-2(POP-Bu-t) (3) and cis,cis-Ru(H-2)Cl-2(POP-Pr-i) (5), respectively. The H-H bond distances are very similar in both compounds, r(H-H) = 1.0 +/- 0.1 angstrom, based on the T-1min and J(HD) data and results of DFT calculations. Reaction of 2 with N-2 gave the dinitrogen complex cis,cis-Ru(N-2)Cl-2(POP-Pr-i) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-Bu-t and POP-iPr complexes 1-6.