chlorido(η-cycloocta-1,5-diene)[tris(2-methoxyphenyl)phosphine]rhodium | 102844-63-3

• 英文名称: chlorido(η-cycloocta-1,5-diene)[tris(2-methoxyphenyl)phosphine]rhodium
• 英文别名: [RhCl(η(4)-1,5-cyclooctadiene)(P(2-OCH3C6H4)3)]；[RhCl(η(4)-COD)(P(2-OCH3C6H4)3)]；RhCl(PAn3)(COD)；RhCl(tris(ortho-anisyl)phospine)(1,5-cyclo-octadiene)
• CAS: 102844-63-3
• 化学式: C₂₉H₃₃ClO₃PRh
• 分子量: 598.911
• InChiKey: JFWIDEBZHKFWOW-ONEVTFJLSA-M

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：

  吡啶 、 ammonium hexafluorophosphate 、 chlorido(η-cycloocta-1,5-diene)[tris(2-methoxyphenyl)phosphine]rhodium 以 甲醇 为溶剂， 以87%的产率得到[Rh(tris(ortho-anisyl)phosphine)(pyridine)(1,5-cyclo-octadiene)]PF6
  参考文献：
  名称：

  Synthesis and characterization of new rhodium and iridium complexes with trianisylphosphine, PAn3, and evaluation of their catalytic behavior in the homogeneous hydrogenation of cinnamaldehyde

  摘要：

  A new family of rhodium and iridium compounds with the bulky tris(ortho-methoxyphenyl) phosphine (PAn(3)) was synthesized and characterized by NMR methods. The X-ray crystal structures of RhCl(PAn(3))(COD)(1) and Ir[(PBz(3))(PAn(3))COD)]PF6 (4) have been determined. A stabilizing agostic interaction has been crystallographically observed in both compounds, due to the steric hindrance of the ortho-substituted phosphine ligand and its presence has been associated to the fluxional behavior shown by the complexes on the NMR timescale in solution. Iridium complexes containing PBz(3) and/or PAn(3) have been evaluated as catalyst precursors for the hydrogenation of trans-cinnamaldehyde (CNA), and their activities have also been compared to those of other iridium complexes containing bulky phosphine ligands, such as PTol(3) (tris-ortho-tolyl-phosphine). The catalytic experiments show that irrespectively of the phosphine combination, all of the evaluated catalysts prevalently hydrogenate the C=C moiety. However, the product selectivity can be tuned by changing either the substrate/catalyst ratio or the phosphine ligand at the metal center. The catalyst with PAn(3) proved to be more efficient and also gave higher yields of the enol product, indicating that stereoelectronic effects are responsible for the changes in selectivity. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2008.11.013
• 作为产物：
  描述：

  三(2-甲氧基苯基)膦 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 丙酮 为溶剂， 以87%的产率得到chlorido(η-cycloocta-1,5-diene)[tris(2-methoxyphenyl)phosphine]rhodium
  参考文献：
  名称：

  三芳基膦对单核铑（I）-氯化物配合物的合成，结构和光谱性质的电子和空间效应

  摘要：

  摘要对双核络合物[{Rh（μ-Cl）（η4-COD）} 2]（COD = 1,5-环辛二烯）与14种不同的三芳基膦之间的反应进行了系统的研究。当使用两个当量的膦时，主要产物是单核络合物[RhCl（η4-COD）（PR3）]，其中R = 4-（OCH3）C6H4（1），4-（CH3）C6H4（2） ，C6H5（3），4-FC6H4（4），4-（CF3）C6H4（5），4-ClC6H4（6），3-（OCH3）C6H4（7），3-（CH3）C6H4（8）， 3-ClC6H4（9），2-（OCH3）C6H4（10），2-（CH3）C6H4（11）和R3 =（C6H5）2（C6F5）（12）。没有贫电子的膦P（C6H5）（C6F5）2和P（C6F5）3不能分离出单核络合物。在双核和单核物质之间观察到溶液中的化学平衡，由于使用笨重的和电子贫乏的膦，不利于单核的形成。单核复合物11

  DOI：

  10.1016/j.poly.2005.10.011

文献信息

• Rhodium-Catalyzed Double Alkyl-Oxygen Bond Cleavage: An Alkyl Transfer Reaction from Bis/Tris(<i>o</i>-alkyloxyphenyl)phosphine to Aryl Acids
  作者：Hui Zhou、Jinlong Zhang、Huameng Yang、Chungu Xia、Gaoxi Jiang

  DOI：10.1021/acs.organomet.6b00638

  日期：2016.10.10

  An unprecedented rhodium-catalyzed selective cleavage of double alkyl-oxygen bonds of bis/tris(o-alkyloxyphenyl)phosphine has been realized, in which P atom functions as a. directing group and simple aryl acids are the methyl group acceptor to provide methyl esters and a quaternary phosphonium salt. The preliminary mechanism was investigated via an O-18 labeling experiment and stoichiometric reaction between a Rh-A crystal and an aromatic acid.