mer-cis-HIr(OH)Cl(PEt3)3 | 161773-21-3

• 英文名称: mer-cis-HIr(OH)Cl(PEt3)3
• CAS: 161773-21-3
• 化学式: C₁₈H₄₇ClIrOP₃
• 分子量: 600.165
• InChiKey: INUWXGDUXUWKAL-UHFFFAOYSA-L

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：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  mer-cis-HIr(OH)Cl(PEt3)3 以 四氢呋喃 为溶剂， 生成 (Cl)Ir(PMe3)3
  参考文献：
  名称：

  Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)₃

  摘要：

  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.

  DOI：

  10.1021/ja012611c
• 作为产物：
  描述：

  [IrCl(PEt3)3] 、 水 以 1,4-二氧六环 为溶剂， 生成 mer-cis-HIr(OH)Cl(PEt3)3
  参考文献：
  名称：

  Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)₃

  摘要：

  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.

  DOI：

  10.1021/ja012611c