mer-cis-HIr(OCH3)Cl(PMe3)3 | 161773-22-4

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: mer-cis-HIr(OCH3)Cl(PMe3)3
• CAS: 161773-22-4
• 化学式: C₁₀H₃₁ClIrOP₃
• 分子量: 487.95
• InChiKey: HBHYMNAWDPAWOT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.59
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  mer-cis-HIr(OCH3)Cl(PMe3)3 在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 mer-cis-HIr(OCH3)2(PMe3)3
  参考文献：
  名称：

  Blum, Ofer; Milstein, David, Journal of the American Chemical Society, 1995, vol. 117, # 16, p. 4582 - 4594

  摘要：

  DOI：
• 作为产物：
  描述：

  在 甲醇 、 氧气 作用下， 生成 mer-cis-HIr(OCH3)Cl(PMe3)3
  参考文献：
  名称：

  Blum, Ofer; Milstein, David, Journal of the American Chemical Society, 1995, vol. 117, # 16, p. 4582 - 4594

  摘要：

  DOI：

文献信息

• Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)₃
  作者：Ofer Blum、David Milstein

  DOI：10.1021/ja012611c

  日期：2002.9.1

  Oxidative addition of aliphatic alcohols to (C8H14)IrCl(PMe3)(3) in benzene yields the cis-hydridoalkoxo products mer-cis-HIr(OR)Cl(PMe3)(3) (R = Me, Et, 1-pentyl, 2-propyl) The analogous hydroxo complex is prepared by oxidative addition of water in THF. The addition rate depends on the nature of the alcohol (methanol > 1-pentanol >> 2-propanol and methanol > water). The reaction is retarded in polar media but accelerated by protic cosolvents. Anionic ligand redistribution involving chloride and alkoxide (or hydroxide) competes with the oxidative addition reaction. A detailed kinetic study suggests that the 16-electron 10(PMe3)(3) is the species undergoing the oxidative addition, and mer-cis-HIr(OR)Cl(PMe3)(3) is the kinetic product. The reaction proceeds by a single-step nucleophilic attack of the metal on the O-H proton pi-Donation by chloride stabilizes the transition state and governs the stereochemical course of the reaction Protic solvent aggregation in the transition state in an apolar medium is suggested mer-cis-HIr(OH)Cl(PEt3)(3), obtained by water addition to IrCl(PEt3)(3), was crystallographically characterized, showing an unusual hydrophobic cage around the hydride ligand.