[Rh(η6-C6H5F)(P(cyclopentyl)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4] | 1033128-87-8

• 英文名称: [Rh(η6-C6H5F)(P(cyclopentyl)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4]
• 英文别名: [Rh(P(cyclo-C5H9)2(η2-C5H7))(η6-C6H5F)][B(C6H3(CF3)2)4]；[Rh(η6-C6H5F)(P(Cyp)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4]；[rhodium(I)(η6-C6H5F)P(Cyp2)(η2-C5H7)]B(C6H3(CF3)2)4
• CAS: 1033128-87-8
• 化学式: C₂₁H₃₀FPRh*C₃₂H₁₂BF₂₄
• 分子量: 1298.57
• InChiKey: LQMXUZWLHSBBLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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(η6-C6H5F)(P(cyclopentyl)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4] 、 二甲胺基甲硼烷 以 further solvent(s) 为溶剂， 以60%的产率得到[rhodium(I)P(Cyp2)(η2-C5H7)(η2-H3BNH(CH3)2)(η1-H3BNH(CH3)2)]B(C6H3(CF3)2)4
  参考文献：
  名称：

  Dallanegra, Romaeo; Chaplin, Adrian B.; Weller, Andrew S., Angewandte Chemie - International Edition, 2009, vol. 48, p. 6875 - 6878

  摘要：

  DOI：
• 作为产物：
  描述：

  [rhodium(I)P(Cyp2)(η2-C5H7)(η2-H3BNH(CH3)2)(η1-H3BNH(CH3)2)]B(C6H3(CF3)2)4 以 氟苯 为溶剂， 生成 [Rh(η6-C6H5F)(P(cyclopentyl)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4]
  参考文献：
  名称：

  Dallanegra, Romaeo; Chaplin, Adrian B.; Weller, Andrew S., Angewandte Chemie - International Edition, 2009, vol. 48, p. 6875 - 6878

  摘要：

  DOI：
• 作为试剂：
  描述：

  甲胺硼烷 在 [Rh(η6-C6H5F)(P(cyclopentyl)2(η2-C5H7))][B(C6H3-3,5-(CF3)2)4] 、 1,2-二氟苯 作用下， 生成 1,3,5-三甲基环硼氮烷
  参考文献：
  名称：

  Dallanegra, Romaeo; Chaplin, Adrian B.; Weller, Andrew S., Angewandte Chemie - International Edition, 2009, vol. 48, p. 6875 - 6878

  摘要：

  DOI：

文献信息

• Amino-borane oligomers bound to a Rh(i) metal fragment
  作者：Romaeo Dallanegra、Adrian B. Chaplin、Jennifer Tsim、Andrew S. Weller

  DOI：10.1039/c003055d

  日期：——

  Coordination complexes of previously observed intermediates, H3B·NMe2BH2·NMe2H and [H2BNMeH]3, in the transition metal catalysed dehydrocoupling of H3B·NMe2H and H3B·NMeH2 have been isolated and structurally characterised using the [RhPR′2(η2-C5H7)}]+ fragment. Their onward reactivity shows that further dehydrogenation is not a simple intramolecular process.

  我们利用[RhPR′2(η2-C5H7)}]+ 片段分离出了在过渡金属催化的 H3B-NMe2H 和 H3B-NMeH2 脱氢偶联反应中先前观察到的中间产物 H3B-NMe2BH2-NMe2H 和 [H2BNMeH]3 的配位配合物，并对其进行了结构表征。它们的继续反应性表明，进一步脱氢并不是一个简单的分子内过程。
• 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.
• Rhodium Phosphine Olefin Complexes of the Weakly Coordinating Anions [BAr^F₄]^- and [1-<i>closo</i>-CB₁₁H₆Br₆]^-. Kinetic versus Thermodynamic Factors in Anion Coordination and Complex Reactivity
  作者：Thomas M. Douglas、Eduardo Molinos、Simon K. Brayshaw、Andrew S. Weller

  DOI：10.1021/om060975d

  日期：2007.1.1

  Solution and solid-state structures for the pair of complexes RhP(Cyp(2))(eta(2)-C5H7)}eta(6)-(C6H3(CF3)(2))BAr3F} and RhP(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.