| 32647-84-0

• CAS: 32647-84-0
• 化学式: C₄₄H₄₁IrO₆P₂
• 分子量: 919.973
• InChiKey: VNXBDURKILXSGR-KEUNEWJHSA-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

• 作为产物：
  描述：

  在 NH₄PF₆ 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  三齿双原金属化亚磷酸三苯酯配合物的第一个实例的合成和单晶X射线结构

  摘要：

  [Ir（cod）（py）2 ] [PF 6 ]与亚磷酸三苯酯反应生成先前报道的络合物[Ir（cod）{P（OC 6 H 4）（OPh）2 {P（OPh）3 }] ，但是[Ir（cod）{P（OPh）3 } Cl]与甲基锂反应，然后用甲醇处理，得到三齿二原金属化配合物[IrH（cod）{P（OC 6 H 4）2（OPh）} ]。

  DOI：

  10.1039/c39950002049

文献信息

• Iridium Complexes of Orthometalated Triaryl Phosphites:  Synthesis, Structure, Reactivity, and Use as Imine Hydrogenation Catalysts
  作者：Robin B. Bedford、Sergio Castillòn、Penny A. Chaloner、Carmen Claver、Elena Fernandez、Peter B. Hitchcock、Aurora Ruiz

  DOI：10.1021/om960239h

  日期：1996.9.17

  Di-orthometalated iridium complexes of triaryl phosphites have been prepared and characterized. The synthesis of the triphenyl phosphite derivative [IrH(cod)P(OC6H4)2(OC6H5)}], 3, requires a circuitous route by treatment of [IrCl(cod)P(OPh)3}] with methyllithium and then methanol. However, with the hindered phosphites P(OAr)3 (Ar = C6H4-2-tBu or C6H3-2,4-tBu2) the di-orthometalated species 5a,b are

  已制备并表征了亚磷酸三芳基酯的二原金属铱配合物。亚磷酸三苯酯衍生物[IrH（cod）P（OC 6 H 4）2（OC 6 H 5）}] 3的合成需要通过[IrCl（cod）P（OPh）3 }]先用甲基锂，再用甲醇。但是，受阻亚磷酸酯P（OAr）3（Ar = C 6 H 4 -2- tBu或C 6 H 3 -2,4- t通过使亚磷酸酯与[Ir（μ-OMe）（cod）} 2 ]或[Ir（cod）（py）2 ] [PF 6 ]反应，可以容易地获得Bu 2）的双正金属化物质5a，b。这些反应的机理已被研究并且是不同的。这两个5A和5B是亚胺加氢催化剂。配合物[IrH 5 P（OAr）3 } 2 ]已从氢化反应中分离出来并独立合成。
• Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution
  作者：Sherzod T. Madrahimov、Qian Li、Ankit Sharma、John F. Hartwig

  DOI：10.1021/jacs.5b08911

  日期：2015.12.2

  Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)(3) was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl](2) and P(OPh)(3) by cydometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.