Rh(norbornadiene)(tricyclopentylphosphine)Cl | 910133-21-0

• 英文名称: Rh(norbornadiene)(tricyclopentylphosphine)Cl
• CAS: 910133-21-0
• 化学式: C₂₂H₃₅ClPRh
• 分子量: 468.852
• InChiKey: YBNQOFBAZZTILG-XDWRCRRRSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Rh(norbornadiene)(tricyclopentylphosphine)Cl 、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 二氯甲烷 为溶剂， 以54%的产率得到Rh(P(Cyp)2(η2-C5H7))(η6-(C6H3(CF3)2)B(C6H3-3,5-(CF3)2)3)
  参考文献：
  名称：

  Rhodium Phosphine Olefin Complexes of the Weakly Coordinating Anions [BAr^F₄]^- and [1-closo-CB₁₁H₆Br₆]^-. Kinetic versus Thermodynamic Factors in Anion Coordination and Complex Reactivity

  摘要：

  Solution and solid-state structures for the pair of complexes Rh{P(Cyp(2))(eta(2)-C5H7)}{eta(6)-(C6H3(CF3)(2))BAr3F} and Rh{P(Cyp(2))(eta(2)-C5H7)}(1-closo-CB11H6Br6), which contain bound weakly coordinating anions, are reported. While thermochemical data show that enthalpically [1-closo-CB11H6Br6](-) binds less strongly with the metal fragment and it is the large entropy loss for the overall process of coordination of the [BAr4F](-) anion that results in the latter anion being thermodynamically more weakly coordinating. Qualitative kinetic data arising from reaction with H-2 indicates that the carborane anion is displaced more readily, attributable to the ability of the carborane to lift a Rh-Br interaction.

  DOI：

  10.1021/om060975d

文献信息

• Rhodium Cyclopentyl Phosphine Complexes of Wide-Bite-Angle Ligands DPEphos and Xantphos
  作者：Romaeo Dallanegra、Adrian B. Chaplin、Andrew S. Weller

  DOI：10.1021/om201034m

  日期：2012.4.9

  Rh(I) and Rh(III) complexes of tricyclopentylphosphine (PCyp(3)), or its dehydrogenated variant PCyp(2)(eta(2)-C5H7), partnered with wide-bite-angle chelating diphosphine ligands DPEphos and Xantphos have been prepared and characterized in solution and the solid state with the aim of studying their potential for reversible dehydrogenation of the PCyp(3) ligand. The complexes fac-[Rh(kappa(3)-P,O,P-L)PCyp2(eta(2)-C5H7)}][BAr4F] (L = DPEphos, Xantphos) show pseudo-trigonal-bipyramidal structures in which the dehydrogenated phosphine alkene ligand acts in a chelating manner. Addition of H-2 to fac-[Rh(id-P,O,P-DPEphos)PCyp2(eta(2)-C5H7)}][BAr4F] resulted in an equilibrium mixture of hydride and hydride-dihydrogen complexes, fac-[Rh(kappa(3)-P,O,P-DPEphos)(H)(2)(PCyp(3))][BAr4F] and [Rh(kappa(2)-P,P-DPEphos)(eta(2)-H-2)(H)(2)(PCyp(3))][BAr4F], in which the DPEphos acts as a hemilabile ligand. For the more rigid Xantphos ligand two dihydride isomers, fac-[Rh(kappa(3)-P,O,P-Xantphos)(H)(2)(PCyp(3))][BAr4F] and mer-[Rh(kappa(3)-P,O,P-Xantphos)(H)(2)(PCyp(3))][BAr4F], are formed, which are also in equilibrium with one another. A van't Hoff analysis of this mixture shows that enthalpically there is very little difference between the two geometries for this system, with the driving force for the preferred far-geometry being entropic. Addition of MeCN to these hydrido complexes results in the central oxygen atom being displaced to form [Rh(kappa(2)-P,P-L)(PCyp(3))(H)(2)(MeCN)][BAr4F], while removal of H-2 from the hydrido complexes (under vacuum or on addition of a hydrogen acceptor) forms the Rh(I) complexes [Rh(kappa(3)-P,O,P-L)(PCyp(3))][BAr4F], which are characterized as having square-planar geometries with meridonial coordination of the respective chelating phosphines. Dehydrogenation of the PCyp3 ligand in these complexes to reform the phosphine-alkene ligands does not occur, even under forcing conditions.