(η(5)-C5Me4H)RhCl2(PPh3) | 244081-45-6

• 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: (η(5)-C5Me4H)RhCl2(PPh3)
• 英文别名: dichlororhodium(1+);1,2,3,4-tetramethylcyclopenta-1,3-diene;triphenylphosphane
• CAS: 244081-45-6
• 化学式: C₂₇H₂₈Cl₂PRh
• 分子量: 557.305
• InChiKey: TXNVOMKOTAAGPF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.46
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (η(5)-C5Me4H)RhCl2(PPh3) 、 苯硼酸 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以83%的产率得到
  参考文献：
  名称：

  [Rh^III(Cp*)]-Catalyzed Cascade Arylation and Chlorination of α-Diazocarbonyl Compounds with Arylboronic Acids and N-Chlorosuccinimide for Facile Synthesis of α-Aryl-α-chloro Carbonyl Compounds

  摘要：

  A Rh(III)-catalyzed cascade arylation and chlorination of alpha-diazocarbonyl compounds with arylboronic acids and N-chlorosuccinimide was achieved. The reaction exhibits excellent functional group tolerance on the organoboron and the diazo reagents; the functionalized alpha-aryl-alpha-chlorocarbonyl compounds were obtained in up to 86% yields. The cascade reaction should involve migratory carbene insertion of arylrhodium(III) to form some reactive rhodium(III)-diketonate complexes. Its subsequent reaction with N-chlorosuccinmide afforded the alpha-chlorocarbonyl products.

  DOI：

  10.1021/acs.orglett.5b00440
• 作为产物：
  描述：

  μ2-dichlorobis(chloro(tetramethylcyclopentadienyl)rhodium) 、 三苯基膦 以 二氯甲烷 为溶剂， 以59%的产率得到(η(5)-C5Me4H)RhCl2(PPh3)
  参考文献：
  名称：

  Phosphine and isonitrile complexes of η5-tetramethylcyclopentadienylrhodium chlorides; crystal structures of (η5-C5Me4H)RhCl2(PPh2R) (R=Ph or C6F5)

  摘要：

  The reaction between [(eta(5)-C5Me4H)RhCl(mu-Cl)](2) and the phosphines PPh2R (R = Ph or C6F5) or cyclohexylisonitrile yields the complexes (eta(5)-C5Me4H)RhCl2L (1, L = PPh3; 2, L = PPh2(C6F3); 3, L = CNC6H11). The structures of complexes 1 and 2 have been determined by single-crystal X-ray diffraction. Both exhibit three-legged piano stool geometry about the rhodium atom. Unlike the structures of (eta(5)-C5Me5)RhCl2L complexes, the rhodium atoms of 1 and 2 do not lie on axes normal to the C-5 centroids, but are displaced towards the CII carbon atoms. Treatment of 1 with cyclohexylisonitrile or 3 with PPh2(C6F5) in the presence of NaBF4, yield the chiral-at-metal salts [(eta(5)-C5Me5)RhCl(PPh2R)(CNC6H11)](+). BF4- as racemic mixtures. The bis(isonitrile) complex, [(eta(5)-C5Me4H)RhCl(CNC6H11)(2)](+). BF4-, is formed similarly from 3. Treatment of [(eta(5)-C5Me4H)RhCl(mu-Cl)](2) with dppe in the presence of NaBF4 yields [(eta(5)-C5Me4H)RhCl(dppe)]+. BF4-. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00151-5