tris[4-{(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)dimethylsilyl}phenyl]phosphine

• 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: tris[4-{(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)dimethylsilyl}phenyl]phosphine
• 英文别名: P(C6H4-p-Si(CH3)2((CH2)2(CF2)7CF3))3；P(p-(Si(CH3)2CH2CH2C8F17)C6H4)3；Tris[4-[3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(dimethyl)silyl]phenyl]phosphane
• 化学式: C₅₄H₄₂F₅₁PSi₃
• 分子量: 1775.08
• InChiKey: LENMXMPZECLZMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  22.39
• 重原子数：
  109
• 可旋转键数：
  33
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  51

反应信息

• 作为反应物：
  描述：

  chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 tris[4-{(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)dimethylsilyl}phenyl]phosphine 以 gas 为溶剂， 生成 RhCl[P(C6H4-p-Si(CH3)2((CH2)2(CF2)7CF3))3]3
  参考文献：
  名称：

  在超临界二氧化碳中均相催化的膜反应器

  摘要：

  提出了一种膜反应器，用于在超临界二氧化碳中进行均相催化并进行原位催化剂分离。该概念提供了良性高密度气体的优点，即在与底物和催化剂相同的相中获得高浓度的气态反应物的可能性，以及通过膜易于催化剂定位的可能性。为了从产物中分离均相催化剂，使用无机微孔膜。使用威尔金森催化剂的氟衍生物[RhCl {P–（C 6 H 4 - p- SiMe 2 CH 2 CH 2 C 8 F 17），可以氢化1-丁烯。3 } 3 ]。威尔金森催化剂的大小为2-4 nm，明显大于二氧化硅膜的孔径0.5-0.8 nm。因此，膜将保留催化剂，而底物和产物则通过膜扩散。在353 K的温度和20 MPa的压力下已实现了稳定的运行并连续生产正丁烷。在32小时的反应中获得了1.2×10 5的周转数。使用紫外可见光谱和ICP-AAS检查催化剂的保留。在膜的渗透侧未检测到铑或磷物质。

  DOI：

  10.1016/s0021-9517(03)00155-6
• 作为产物：
  描述：

  1-bromo-4-[3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(dimethyl)silyl]benzene 在 正丁基锂 、 lithium bromide 、 三甲氧基磷 作用下， 以 正己烷 、 正戊烷 为溶剂， 反应 15.0h， 以48%的产率得到tris[4-{(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)dimethylsilyl}phenyl]phosphine
  参考文献：
  名称：

  Synthesis and Properties of a Novel Family of Fluorous Triphenylphosphine Derivatives

  摘要：

  A novel approach to the preparation of perfluorotail-functionalized triarylphosphines using a p-silyl substituent as the branching point has been developed. This approach enabled the attachment of between three and nine perfluarotails per phosphorus atom, resulting in the production of highly fluorous tris [p-(1H,1H,2H,2H-perfluoroalkylsilyl)aryl] phosphines, P[C6H4-p-SiMe3-n(CH2CH2CxF2x+1)(n)](3) (n = 1, 2, 3; x = 6, 8), containing between 50 and 67 wt % nuorine. P-31 NMR studies indicate that the phosphorus atoms, and consequently the a-donor and pi-acceptor properties of these phosphines, are not influenced by the electron-withdrawing perfluoroalkyltails. The fluorous triarylphosphines are readily soluble in fluorous solvents and display fluorous phase preference in several fluorous biphasic systems. The phase partitioning of these fluorous ligands, as well as their donor properties, is discussed in relation to their potential for fluorous biphasic catalyst separation.

  DOI：

  10.1021/jo991548v

文献信息

• Fluorous Versions of Wilkinson's Catalyst. Activity in Fluorous Hydrogenation of 1-Alkenes and Recycling by Fluorous Biphasic Separation
  作者：Bodo Richter、Anthony L. Spek、Gerard van Koten、Berth-Jan Deelman

  DOI：10.1021/ja993562v

  日期：2000.4.1

  Wilkinson's catalyst show high activity in hydrogenation of 1-alkenes under single phase fluorous conditions and can be effectively recycled using the new concept of fluorous biphasic separation. For comparison the p-(trimethylsilyl)-substituted derivative RhCl(P(C6H4-p-SiMe3)3)3 (3c) has also been synthesized and the X-ray structure of dimeric (Rh(I-Cl)P(C6H4- p-SiMe3)3}2)2 (4c) was determined. A comparison

  两种新型氟三（芳基膦）氯化铑 (I) 络合物 RhCl(PC6H4-p-SiMe2- (CH2)2CnF2n+1}3)3 (3a: n ) 6, 3b: n ) 8) 是Wilkinson 的催化剂在单相含氟条件下对 1-烯烃的加氢显示出高活性，并且可以使用含氟双相分离的新概念有效回收。为了比较，还合成了对（三甲基甲硅烷基）取代的衍生物 RhCl(P(C6H4-p-SiMe3)3)3 (3c) 和二聚体 (Rh(I-Cl)P(C6H4) 的 X 射线结构- 确定了 p-SiMe3)3}2)2 (4c)。氟催化剂和非氟衍生物在相同条件下的催化活性的比较显示，活性按照 3c > 3a > RhCl- (PPh3)3 > 3b 的顺序降低。新型催化剂的回收效率（> 根据游离膦配体本身的氟相亲和力，3b) 的 98% 比预期的要好得多，实际上这是由于在此期间和之后存在的含膦铑物质的氟相亲和力高
• Homogeneous Reactions in Supercritical Carbon Dioxide Using a Catalyst Immobilized by a Microporous Silica Membrane
  作者：Leo J. P. van den Broeke、Earl L. V. Goetheer、Arjan W. Verkerk、Elwin de Wolf、Berth-Jan Deelman、Gerard van Koten、Jos T. F. Keurentjes

  DOI：10.1002/1521-3773(20011203)40:23<4473::aid-anie4473>3.0.co;2-0

  日期：2001.12.3
• Fluorous biphasic hydrogenation of 1-alkenes using novel fluorous derivatives of Wilkinson's catalyst
  作者：Bodo Richter、Berth-Jan Deelman、Gerard van Koten

  DOI：10.1016/s1381-1169(99)00149-1

  日期：1999.9

  A novel approach for the easy attachment of fluorous tails to aryl phospines has been developed, leading to a new fluorous alkylsilyl-substituted triaryl phospines P(C6H4SiMe2Rf-4)(3)(R-f = -(CH2)(2)(CF2)(n)CF3; n= 5, 7). The derived fluorous tris(aryl phospine)rhodium(I) chloride complexes, being fluorous analogs of Wilkinson's catalyst, show high activity in hydrogeneration of 1-alkenes under fluorous biphasic (FBS) conditions and can be effectively recycled. (C) 1999 Elsevier Science B.V. All rights reserved.
• Synthesis and Properties of a Novel Family of Fluorous Triphenylphosphine Derivatives
  作者：Bodo Richter、Elwin de Wolf、Gerard van Koten、Berth-Jan Deelman

  DOI：10.1021/jo991548v

  日期：2000.6.1

  A novel approach to the preparation of perfluorotail-functionalized triarylphosphines using a p-silyl substituent as the branching point has been developed. This approach enabled the attachment of between three and nine perfluarotails per phosphorus atom, resulting in the production of highly fluorous tris [p-(1H,1H,2H,2H-perfluoroalkylsilyl)aryl] phosphines, P[C6H4-p-SiMe3-n(CH2CH2CxF2x+1)(n)](3) (n = 1, 2, 3; x = 6, 8), containing between 50 and 67 wt % nuorine. P-31 NMR studies indicate that the phosphorus atoms, and consequently the a-donor and pi-acceptor properties of these phosphines, are not influenced by the electron-withdrawing perfluoroalkyltails. The fluorous triarylphosphines are readily soluble in fluorous solvents and display fluorous phase preference in several fluorous biphasic systems. The phase partitioning of these fluorous ligands, as well as their donor properties, is discussed in relation to their potential for fluorous biphasic catalyst separation.
• Membrane reactor for homogeneous catalysis in supercritical carbon dioxide
  作者：Earl L.V. Goetheer、Arjan W. Verkerk、Leo J.P. van den Broeke、Elwin de Wolf、Berth-Jan Deelman、Gerard van Koten、Jos T.F. Keurentjes

  DOI：10.1016/s0021-9517(03)00155-6

  日期：2003.10.1

  homogeneous catalysis in supercritical carbon dioxide with in situ catalyst separation. This concept offers the advantages of benign high-density gases, i.e., the possibility of achieving a high concentration of gaseous reactants in the same phase as the substrates and catalyst as well as easy catalyst localization by means of a membrane. For the separation of the homogeneous catalyst from the products

  提出了一种膜反应器，用于在超临界二氧化碳中进行均相催化并进行原位催化剂分离。该概念提供了良性高密度气体的优点，即在与底物和催化剂相同的相中获得高浓度的气态反应物的可能性，以及通过膜易于催化剂定位的可能性。为了从产物中分离均相催化剂，使用无机微孔膜。使用威尔金森催化剂的氟衍生物[RhCl P–（C 6 H 4 - p- SiMe 2 CH 2 CH 2 C 8 F 17），可以氢化1-丁烯。3 } 3 ]。威尔金森催化剂的大小为2-4 nm，明显大于二氧化硅膜的孔径0.5-0.8 nm。因此，膜将保留催化剂，而底物和产物则通过膜扩散。在353 K的温度和20 MPa的压力下已实现了稳定的运行并连续生产正丁烷。在32小时的反应中获得了1.2×10 5的周转数。使用紫外可见光谱和ICP-AAS检查催化剂的保留。在膜的渗透侧未检测到铑或磷物质。