| 154625-83-9

• CAS: 154625-83-9
• 化学式: C₂₈H₄₈BrIrP₂
• 分子量: 718.761
• InChiKey: WEVKPZVOUIRXSZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.09
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  、 cesium fluoride 在 18-冠醚-6 作用下， 以 苯 为溶剂， 生成 bis(di-tert-butyl(phenyl)-l5-phosphaneyl)iridium(V) fluoride dihydride
  参考文献：
  名称：

  Hauger, Bryan E.; Gusev, Dmitry; Caulton, Kenneth G., Journal of the American Chemical Society, 1994, vol. 116, # 1, p. 208 - 214

  摘要：

  DOI：
• 作为产物：
  描述：

  sodium bromide 、 Ir(H)2Cl(P(t)Bu2Ph)2 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Identification of an elusive catalyst: IrH(η2-C6H4PtBu2) (Cl)(PtBu2Ph) as a precursor for C=C bond migration

  摘要：

  The catalytic isomerization of allylbenzene to cis/trans-beta-Me styrene in solutions containing Ir(III) hydride halide, hydride hydroxide and hydride alkoxide Ir(H)(2)X(P(t)Bu(2)Ph)(2)(X=F, Cl, Br, I, OH, OCH2CF3) is described. Large variations in isomerization rate (k(obs)) are found to correlate with the electron donating ability (pi + sigma) of the X ligand: the rate is enhanced by more effective donation by the X Ligands. A number of kinetic studies and phosphine exchange experiments utilizing a deuterium labeled phosphine, P(t)Bu(2)(d(5))Ph, indicate that the active isomerization catalyst is a 14-valence-electron Ir(III) species derived from the ortha-metallated complex, IrH(eta(2)-C(6)H(4)P(t)Bu(2))(X) (P(t)Bu(2)Ph), by phosphine dissociation. Using IrH(eta(2)-C(6)H(4)P(t)Bu(2)) (Cl)(P(t)Bu(2)Ph) as a catalyst precursor, the catalytic isomerization of alpha,alpha-d(2)-allylbenzene in the presence of an excess of 4-allyl anisole has yielded primarily d(1)-cis/trans-beta-Me styrene, which confirms that the isomerization proceeds via an insertion-elimination mechanism of a metal hydride bond.

  DOI：

  10.1016/s0020-1693(96)05249-8

文献信息

• HX elimination from Ir(H)2X(PBu2tPh)2 promoted by CO coordination: assessment of X ligand influence
  作者：Alan C. Cooper、John C. Bollinger、John C. Huffman、Kenneth G. Caulton

  DOI：10.1039/a800525g

  日期：——

  crystalline [Ir(H)2(CO)2(PBu2tPh)2][SiF5] and [Ir(CO)2(PBu2tPh)2][SiF5]·C6D6, both characterized by X-ray diffraction. The latter, although approximately square planar, has a C–Ir–C angle of only 162.7°. Crystallographic data (Pc at -165 °C) for [Ir(H)2(CO)2(PBu2tPh)2][SiF5], a=8.293(2), b=12.462(5), c=16.333(7) Å, β=98.21(2)° with Z=2. Crystallographic data (P21/n at -172 °C) for [Ir(CO)2(PBu2tPh)2][SiF5]·C6D6

  配位不饱和配合物Ir（H）2 X（PBu 2 t Ph）2 [X = Cl，Br，I，N 3，N C NSiMe 3，NHC（O）CH 3，OC（O）CF 3，OSO 2 CF 3，OC（O）CH 3，SPh，OPh，F]均在混合时间内在芳烃溶剂中反应以结合一氧化碳。这些CO加合物随后还原性消除HX的反应性取决于配体pπ轨道和金属dπ轨道之间的填充-排斥反应所引起的固有不稳定程度。这种不稳定不是当X = Cl，Br，I，N 3，N C NSiMe 3，NHC（O）CH 3或OC（O）CF 3时，足以促进HX的损失。当X = OC（O）CH 3或SPh时，形成亚稳的CO加合物，最终失去HX。含有OPh或F的配合物在与CO反应后迅速失去HX。不寻常的铱（I）配合物IrH（CO）2（PBu 2 t Ph）和IrH（CO）（PBu 2 t Ph）2已通过多核NMR进行了表征和红外光谱。Ir（H）2（F）（PBu