1,2-bis[bis{4-((2-(perfluorohexyl)ethyl)dimethylsilyl)phenyl}phosphino]ethane

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,2-bis[bis{4-((2-(perfluorohexyl)ethyl)dimethylsilyl)phenyl}phosphino]ethane
• 英文别名: 2-Bis[4-[dimethyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]phenyl]phosphanylethyl-bis[4-[dimethyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]phenyl]phosphane
• 化学式: C₆₆H₆₀F₅₂P₂Si₄
• 分子量: 2015.41
• InChiKey: AHOSOEIDTMYPOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  25.43
• 重原子数：
  124
• 可旋转键数：
  39
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  52

反应信息

• 作为反应物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 1,2-bis[bis{4-((2-(perfluorohexyl)ethyl)dimethylsilyl)phenyl}phosphino]ethane 以 二氯甲烷 为溶剂， 以95%的产率得到2-bis[4-[dimethyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]phenyl]phosphanylethyl-bis[4-[dimethyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]phenyl]phosphane;dichloropalladium
  参考文献：
  名称：

  1H,1H,2H,2H-Perfluoroalkyl-Functionalization of Ni(II), Pd(II), and Pt(II) Mono- and Diphosphine Complexes:  Minimizing the Electronic Consequences for the Metal Center

  摘要：

  A series of fluorous derivatives of group 10 complexes MCl2(dppe) and [M(dppe)(2)](BF4)(2) (M = Ni, Pd or Pt; dppe = 1,2-bis(diphenylphosphino)ethane) and cis-PtCl2(PPh3)(2) was synthesized. The influence of para-(1H,1H,2H,2H-perfluoroalkyl)dimethylsilyl-functionalization of the phosphine phenyl groups of these complexes, as studied by NMR spectroscopy, cyclovoltammetry (CV), XPS analyses, as well as DFT calculations, points to a weak steric and no significant inductive electronic effect. The steric effect is most pronounced for M = Ni and leads in the case of NiCl2(1c) (3c) and [Ni(1c)(2)](BF4)(2) (7c) (1c = [CH2P{C6H4(SiMe2CH2CH2C6F13)-4}(2)](2)) to a tetrahedral distortion from the expected square planar geometry. The solubility behavior of NiCl2[CH2P{C6H4(SiMe3-b(CH2CH2CxF2x+1)b)4}(2)](2) (3: b = 1-3; x = 6, 8) in THF, toluene, and c-C6F11CF3 was found to follow the same trends as those observed for the free fluorous ligands 1. A similar correlation between the partition coefficient (P) of complexes 3 and free 1 was observed in fluorous biphasic solvent systems, with a maximum value obtained for 3f (b = 3, x 6, P = 23 in favor of the fluorous phase).

  DOI：

  10.1021/ic025770l
• 作为产物：
  描述：

  1H,1H,2H,2H-全氟辛基二甲基氯硅烷 、 1,2-bis[bis(4-bromophenyl)phosphino]ethane 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 7.5h， 以85%的产率得到1,2-bis[bis{4-((2-(perfluorohexyl)ethyl)dimethylsilyl)phenyl}phosphino]ethane
  参考文献：
  名称：

  1,2-双（二苯基膦基）乙烷的高氟衍生物

  摘要：

  DOI：

  10.1021/jo000312k

文献信息

• 1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-Perfluoroalkyl-Functionalization of Ni(II), Pd(II), and Pt(II) Mono- and Diphosphine Complexes:  Minimizing the Electronic Consequences for the Metal Center
  作者：Elwin de Wolf、Ad J. M. Mens、Onno L. J. Gijzeman、Joop H. van Lenthe、Leonardus W. Jenneskens、Berth-Jan Deelman、Gerard van Koten

  DOI：10.1021/ic025770l

  日期：2003.3.1

  A series of fluorous derivatives of group 10 complexes MCl2(dppe) and [M(dppe)(2)](BF4)(2) (M = Ni, Pd or Pt; dppe = 1,2-bis(diphenylphosphino)ethane) and cis-PtCl2(PPh3)(2) was synthesized. The influence of para-(1H,1H,2H,2H-perfluoroalkyl)dimethylsilyl-functionalization of the phosphine phenyl groups of these complexes, as studied by NMR spectroscopy, cyclovoltammetry (CV), XPS analyses, as well as DFT calculations, points to a weak steric and no significant inductive electronic effect. The steric effect is most pronounced for M = Ni and leads in the case of NiCl2(1c) (3c) and [Ni(1c)(2)](BF4)(2) (7c) (1c = [CH2PC6H4(SiMe2CH2CH2C6F13)-4}(2)](2)) to a tetrahedral distortion from the expected square planar geometry. The solubility behavior of NiCl2[CH2PC6H4(SiMe3-b(CH2CH2CxF2x+1)b)4}(2)](2) (3: b = 1-3; x = 6, 8) in THF, toluene, and c-C6F11CF3 was found to follow the same trends as those observed for the free fluorous ligands 1. A similar correlation between the partition coefficient (P) of complexes 3 and free 1 was observed in fluorous biphasic solvent systems, with a maximum value obtained for 3f (b = 3, x 6, P = 23 in favor of the fluorous phase).
• Highly Fluorous Derivatives of 1,2-Bis(diphenylphosphino)ethane
  作者：Elwin de Wolf、Bodo Richter、Berth-Jan Deelman、Gerard van Koten

  DOI：10.1021/jo000312k

  日期：2000.8.1