fac-IrH3(CO)(1,2-bis(diphenylphosphino)ethane) | 85421-67-6

• 英文名称: fac-IrH3(CO)(1,2-bis(diphenylphosphino)ethane)
• CAS: 85421-67-6
• 化学式: C₂₇H₂₇IrOP₂
• 分子量: 621.678
• InChiKey: YMEMGEUMWKAZPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 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：

  fac-IrH3(CO)(1,2-bis(diphenylphosphino)ethane) 以 苯 为溶剂， 生成 氢气
  参考文献：
  名称：

  Fisher, Barbara J.; Eisenberg, Richard, Organometallics, 1983, vol. 2, # 6, p. 764 - 767

  摘要：

  DOI：
• 作为产物：
  描述：

  IrI(CO)(1,2-bis(diphenylphosphino)ethane) 在 sodium tetrahydroborate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 以90%的产率得到fac-IrH3(CO)(1,2-bis(diphenylphosphino)ethane)
  参考文献：
  名称：

  Fisher, Barbara J.; Eisenberg, Richard, Organometallics, 1983, vol. 2, # 6, p. 764 - 767

  摘要：

  DOI：

文献信息

• Synthesis and reactivity of ethyliridium complexes. Reductive elimination of carbon-hydrogen and hydrogen-hydrogen bonds from an ethyldihydridoiridium complex
  作者：Paul P. Deutsch、Richard Eisenberg

  DOI：10.1021/ja00158a033

  日期：1990.1

  Cinetique de l'elimination reductrice concurrente de C 2 H 6 et H 2 , de IrH 2 (Et)(CO)(dppe)

  C 2 H 6 et H 2 , de IrH 2 (Et)(CO)(dppe) 的消除还原同时发生
• Stereoselective oxidative addition of silanes and hydrogen halides to the iridium(I) cis phosphine complexes IrX(CO)(dppe) (X = Br, CN; dppe = 1,2-bis(diphenylphosphino)ethane)
  作者：Curtis E. Johnson、Richard Eisenberg

  DOI：10.1021/ja00309a019

  日期：1985.11

  Formation possible de 4 diastereomeres. Cinetique des isomerisations. Il semblerait que l'approche du silane au complexe d'In (I) soit nucleophile, celle de HX etant electrophile

  可能形成 de 4 非对映异构体。Cinetique des 异构化。Il semblerait que l'approche du 硅烷 au complexe d'In (I) soit 亲核试剂，celle de HX etant 亲电试剂
• Stereoselective oxidative addition of hydrogen to iridium(I) complexes. Kinetic control based on ligand electronic effects
  作者：Curtis E. Johnson、Richard Eisenberg

  DOI：10.1021/ja00297a021

  日期：1985.5

  of H2 to the iridium(I) chelates IrX(CO) (dppe) (X(-) = Cl(-), Br(-), I(-), Cn(-), H(-), PPh3; dppe = 1, 2-bis-(diphenylphosphino)ethane) proceeds with > 99% steroselectivity to yield a cis dihydride product with one hydride trans to P(dppe) and the other hydride trans to CO. For X = Cl, Br, and I, the kinetic product of formula IrH2X(CO)(dppe) equilibrates with a more stable cis isomer which has one

  摘要 : H2 氧化加成到铱 (I) 螯合物 IrX(CO) (dppe) (X(-) = Cl(-), Br(-), I(-), Cn(-), H(-) ), PPh3; dppe = 1, 2-双-(二苯基膦基)乙烷) 以 > 99% 的立体选择性产生顺式二氢化物产物，其中一个氢化物反式为 P(dppe)，另一个氢化物反式为 CO。对于 X = Cl 、Br 和 I，式 IrH2X(CO)(dppe) 的动力学产物与更稳定的顺式异构体平衡，其中一个氢化物与 P 反式，另一个与 X 反式（K sub eq = 41、35 和 13，分别）。通过对 X = Br 的热力学异构体进行单晶 X 射线衍射分析，证实了基于氢化物配体化学位移的立体化学分配。复杂的 IrH2Br(CO)(dppe) 在正交空间群中结晶。两种二氢化物异构体之间的异构化反应已在丙酮和苯溶剂中进行了机械研究。在丙酮中，IrH2Br(CO)(dppe)
• Hays, Mary K.; Eisenberg, Richard, Inorganic Chemistry, 1991, vol. 30, # 12, p. 2623 - 2630
  作者：Hays, Mary K.、Eisenberg, Richard

  DOI：——

  日期：——
• Oxidative addition of catecholborane to IrX(CO)(dppe) complexes
  作者：Brian P. Cleary、Richard Eisenberg

  DOI：10.1021/om00010a017

  日期：1995.10

  The oxidative addition of catecholborane (1,3,2-benzodioxaborole) to the Ir(I) cis-phosphine complexes IrX(CO)(dppe) (X = Br, I, H, BO2C6H4; dppe = 1,2-bis(diphenylphosphino)ethane) has been found to proceed stereoselectively under kinetic control. Of the four complexes that can be formed by cis oxidative addition of the B-H bond to IrBr(CO)(dppe), the one having hydride trans to phosphorus and boron trans to bromide is formed in >99% yield while addition to IrI(CO)(dppe) occurs similarly but with only 90% stereoselectivity. Isomerization of the initially formed diastereomers to thermodynamically less stable diastereomers which display hydride trans to halide and boron trans to phosphorus occurs after 1 day. The mechanism for the isomerism for X = Br has been determined to proceed via reductive elimination/oxidative addition processes. The oxidative addition reactions of catecholborane to [IrH(CO)(dppe)] and [Ir(BO2C6H4)(CO)(dppe)], generated from IrH3(CO)(dppe) and IrH2(BO2C6H4)(CO)(dppe), respectively, also occur in a cis fashion with 99% stereoselectivity yielding Ir(III) products with hydride trans to CO and boron trans to phosphorus. The observed stereoselectivity for catecholborane addition to IrX(CO)(dppe) (X = Br, I) is reversed with respect to addition to IrX(CO)(dppe) (X = H, BO2C6H4) and is accounted for by electronic factors involving the pi-basicity of the halide ligands.