(η5-cyclopentadienyl)(trimethylphosphine)rhodium dihydride | 104337-98-6

• 英文名称: (η5-cyclopentadienyl)(trimethylphosphine)rhodium dihydride
• 英文别名: [Rh(η(5)-C5H5)(PMe3)(H)2]；CpRhH2PMe3
• CAS: 104337-98-6
• 化学式: C₈H₁₆PRh
• 分子量: 246.094
• InChiKey: MMBGNAXGUXHZBF-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  (η5-cyclopentadienyl)(trimethylphosphine)rhodium dihydride 在 一氧化碳 作用下， 以 solid matrix 为溶剂， 生成 (cyclopentadienyl)(rhodium)(carbonyl){trimethylphosphine}
  参考文献：
  名称：

  Photochemical generation of 16-electron [Rh(η⁵)-C₅H₅)-(PMe₃)] and [Ir(η⁵-C₅H₅)(PMe₃)] in low-temperature matrices: evidence for methane activation

  摘要：

  The photochemical reactions of [Rh(eta(5)-C5H5)(PMe(3))(H)(2)] and [Ir(eta(5)-C5H5)(PMe(3))(H)(2)] have been studied in Ar, CH4, N-2 and CO-doped argon matrices by IR and UV/VIS spectroscopy. The UV photolysis in argon matrices results in the formation of the 16-electron complexes [M(eta(5)-C5H5)(PMe(3))] with characteristic visible absorption maxima (M = Rh, lambda(max) 399 and 488 nm; M = Ir, lambda(max) 436 and 526 nm). The reaction is partially reversed by long-wavelength photolysis. The conversion of [Rh(eta(5)-C5H5)(PMe(3))(H)(2)] to [Rh(eta(5)-C5H5)(PMe(3))(Me)H] on photolysis in methane matrices is confirmed by extensive isotopic labelling studies and by the use of alternative precursors for the methyl hydride, viz. [Rh(eta(5)-C5H5)(PMe(3))(eta(2)-C6F6)] and [Rh(eta(5)-C5H5)(PMe(3))(C2H4)]. Evidence has also been obtained to show that irradiation of [Ir(eta(5)-C5H5)(PMe(3))(H)(2)] in methane yields [Ir(eta(5)-C5H5)(PMe(3))(Me)H]. Photolysis of [M(eta(5)-C5H)(PMe(3))(H)2] in N-2 and CO-doped Ar matrices generates [M(eta(5)-C5H5)(PMe(3))L] (M = Rh or Ir, L = N-2 or CO).

  DOI：

  10.1039/dt9940003519
• 作为产物：
  描述：

  [Rh(η(5)-C5H5)(PMe3)] 以 solid matrix 为溶剂， 生成 (η5-cyclopentadienyl)(trimethylphosphine)rhodium dihydride
  参考文献：
  名称：

  Photochemical generation of 16-electron [Rh(η⁵)-C₅H₅)-(PMe₃)] and [Ir(η⁵-C₅H₅)(PMe₃)] in low-temperature matrices: evidence for methane activation

  摘要：

  The photochemical reactions of [Rh(eta(5)-C5H5)(PMe(3))(H)(2)] and [Ir(eta(5)-C5H5)(PMe(3))(H)(2)] have been studied in Ar, CH4, N-2 and CO-doped argon matrices by IR and UV/VIS spectroscopy. The UV photolysis in argon matrices results in the formation of the 16-electron complexes [M(eta(5)-C5H5)(PMe(3))] with characteristic visible absorption maxima (M = Rh, lambda(max) 399 and 488 nm; M = Ir, lambda(max) 436 and 526 nm). The reaction is partially reversed by long-wavelength photolysis. The conversion of [Rh(eta(5)-C5H5)(PMe(3))(H)(2)] to [Rh(eta(5)-C5H5)(PMe(3))(Me)H] on photolysis in methane matrices is confirmed by extensive isotopic labelling studies and by the use of alternative precursors for the methyl hydride, viz. [Rh(eta(5)-C5H5)(PMe(3))(eta(2)-C6F6)] and [Rh(eta(5)-C5H5)(PMe(3))(C2H4)]. Evidence has also been obtained to show that irradiation of [Ir(eta(5)-C5H5)(PMe(3))(H)(2)] in methane yields [Ir(eta(5)-C5H5)(PMe(3))(Me)H]. Photolysis of [M(eta(5)-C5H)(PMe(3))(H)2] in N-2 and CO-doped Ar matrices generates [M(eta(5)-C5H5)(PMe(3))L] (M = Rh or Ir, L = N-2 or CO).

  DOI：

  10.1039/dt9940003519
• 作为试剂：
  描述：

  1-苄基-吡咯烷 、 碘苯 在 (η5-cyclopentadienyl)(trimethylphosphine)rhodium dihydride 作用下， 以 叔丁醇 为溶剂， 以22%的产率得到1-二苯甲基吡咯烷
  参考文献：
  名称：

  N-苯基吡咯烷的选择性和催化芳基化：没有导向基团的 sp3C-H 键官能化

  摘要：

  我们在此描述了我们对 N-苯基吡咯烷的芳基化的研究，这导致了在没有导向基团的情况下 sp3 CH 键的直接和选择性芳基化的新转化的发展。该方法以 Ru(H)2(CO)(PCy3)3 4 为催化剂，初步机理研究表明 Ru(Ph)(I)(CO)(PCy3)2 5 是该反应的关键中间体。催化循环。观察到大的动力学同位素效应 (kH/kD = 5.4)，这支持 CH 键金属化是缓慢步骤的提议。底物范围的初步检查表明，除了 N-苯基吡咯烷，N-甲基-和 N-苄基吡咯烷以及 N-苯甲酰基吡咯烷在反应条件下也被芳基化。

  DOI：

  10.1021/ja050269o

文献信息

• Mechanism of Carbon−Fluorine Bond Activation by (C₅Me₅)Rh(PMe₃)H₂
  作者：Brian L. Edelbach、William D. Jones

  DOI：10.1021/ja970723r

  日期：1997.8.1

  The complex Cp*Rh(PMe3)H2 (Cp* = C5Me5) reacts with C6F6, C6F5H, C12F10, or C10F8 in pyridine or 1:1 pyridine/benzene to give the C−F cleavage products Cp*Rh(PMe3)(arylF)H in high yield. Kinetic studies reveal that the reaction has autocatalytic character, and fluoride ion is shown to be responsible for the catalysis. The anion [Cp*Rh(PMe3)H]- reacts rapidly with C12F10 or C10F8 to give the same C−F

  复合物 Cp*Rh(PMe3)H2 (Cp* = C5Me5) 与 C6F6、C6F5H、C12F10 或 C10F8 在吡啶或 1:1 吡啶/苯中反应，得到 C-F 裂解产物 Cp*Rh(PMe3)(芳基 F )H 高产。动力学研究表明该反应具有自催化特性，并且氟离子被证明是催化作用的原因。阴离子 [Cp*Rh(PMe3)H]- 与 或 快速反应，产生与 Cp*Rh(PMe3)H2 相同的 C-F 裂解产物。提出了一种由 Cp*Rh(PMe3)H2 的去质子化引发的机制，然后是所得阴离子对多氟芳烃的亲核攻击，随后失去氟化物。氟离子通过去质子化 Cp*Rh(PMe3)H2 继续循环。
• Chin, R. Martin; Dong, Lingzhen; Duckett, Simon B., Journal of the American Chemical Society, 1993, vol. 115, # 17, p. 7685 - 7695
  作者：Chin, R. Martin、Dong, Lingzhen、Duckett, Simon B.、Partridge, Martin G.、Jones, William D.、Perutz, Robin N.

  DOI：——

  日期：——
• Isomerization of the hydridoalkylrhodium complexes formed on oxidative addition of rhodium to alkane carbon-hydrogen bonds. Evidence for the intermediacy of .eta.2-alkane complexes
  作者：Roy A. Periana、Robert G. Bergman

  DOI：10.1021/ja00283a032

  日期：1986.11