[(triphos)Rh(η1-THF-d8)H2](1+) | 264624-47-7

• 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: [(triphos)Rh(η1-THF-d8)H2](1+)
• 英文别名: [RhH2(THF-d8-κO)(triphos)](1+)
• CAS: 264624-47-7
• 化学式: C₄₅H₄₉OP₃Rh
• 分子量: 809.647
• InChiKey: JUCSFOVIHNIMIJ-ZWXZEGSZSA-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

• 作为产物：
  描述：

  氘代四氢呋喃 、 RhH3(triphos) 、 氟硼酸二甲基醚络合物 以 氘代四氢呋喃 为溶剂， 生成 [(triphos)Rh(η2-H2)H2](1+) 、 [(triphos)Rh(η1-THF-d8)H2](1+)
  参考文献：
  名称：

  ¹H- and ²H-T₁ Relaxation Behavior of the Rhodium Dihydrogen Complex [(Triphos)Rh(η²-H₂)H₂]⁺

  摘要：

  Protonation of the classical trihydride [(triphos)RhH3] (2) at 210 K in either THF or CH2Cl2 by either HBF4. OMe2 or CF3SO2OH gives the nonclassical eta(2)-H-2 complex [(triphos)Rh(eta(2)-H-2)H-2](+) (1) [triphos = MeC(CH2PPh2)(3)]. Complex 1 is thermally unstable and highly fluxional in solution. In THF above 230 K, 1 transforms into the solvento dihydride complex [(triphos)Rh(eta(1)-THF-d(8))H-2](+) (5) that, at room temperature, quickly converts to the stable dimer trans-[{(triphos)RhH}(2)(mu-H)(2)](2+) (trans-6). In CH2Cl2, 1 is stable up to 240 K. Above this temperature, the eta(2)-H-2 complex begins to convert into a mixture of trans- and cis-6, which, in turn, transform into the bridging chloride dimers trans- and cis-[{(triphos)RhH}(2)(mu-Cl)(2)](2+) at room temperature. Complex 1 contains a fast-spinning H-2 ligand with a T-1min of 38.9 ms in CD2Cl2 (220 K, 400 MHz). An NMR analysis of the bis-deuterated isotopomer [(triphos)RhH2D2](+) (1-d(2)) did not provide a J(HD) value. At 190 K, the perdeuterated isotopomers [(triphos)RhD3] (2-d(3)) and 1-d(4) show T-1min, values of 16.5 and 32.6 ms (76.753 MHZ), respectively, for the rapidly exchanging deuterides. An analogous 2-fold elongation of T-1min, is also observed on going from [(triphos)IrD3] to [(triphos)Ir(eta(2)-D-2)D-2](+). A rationale for the elongation of T-1min, in nonclassical polyhydrides is proposed on the basis of both the results obtained and recent literature reports.

  DOI：

  10.1021/ic990667q

文献信息

• Hydrogenation of Quinoline by Rhodium Catalysts Modified with the Tripodal Polyphosphine Ligand MeC(CH2PPh2)3
  作者：Claudio Bianchini、Pierluigi Barbaro、Michela Macchi、Andrea Meli、Francesco Vizza

  DOI：10.1002/1522-2675(20011017)84:10<2895::aid-hlca2895>3.0.co;2-0

  日期：2001.10.17

  As part of our modelling studies of the hydrodenitrogenation of N-heterocycles contained in raw oil materials, we investigated the selective hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline by rhodium catalysts modified with the tripodal polyphosphane ligand MeC(CH2PPh2)3. Experiments in standard autoclaves and in high-pressure sapphire NMR tubes, kinetic and isotope labelling studies, and

  作为我们对原料中所含 N-杂环的加氢脱氮建模研究的一部分，我们研究了用三足多膦配体 MeC(CH2PPh2)3 改性的铑催化剂将喹啉选择性加氢为 1,2,3,4-四氢喹啉。 . 在标准高压釜和高压蓝宝石核磁共振管中的实验、动力学和同位素标记研究以及与孤立化合物的独立反应有助于阐明催化机制以及确定金属催化剂的电子要求，以实现选择性和高效氢化。