tetrakis(trimethyl-l5-phosphaneyl)iridium(VII) chloride dihydride | 83380-23-8

• 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: tetrakis(trimethyl-l5-phosphaneyl)iridium(VII) chloride dihydride
• CAS: 83380-23-8；1375081-19-8
• 化学式: C₁₂H₃₈IrP₄*Cl
• 分子量: 534.002
• InChiKey: NPYHTTHOYHJXCQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18.0
• 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：
  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：

  tetrakis(trimethyl-l5-phosphaneyl)iridium(VII) chloride dihydride 在 potassium tert-butoxide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 hydrido((trimethylsiloxy)methyl)tetrakis(trimethylphosphine)iridium(III) iodide
  参考文献：
  名称：

  Thorn, David L.; Tulip, Organometallics, 1982, vol. 1, # 12, p. 1580 - 1586

  摘要：

  DOI：
• 作为产物：
  描述：

  [Ir(PMe3)4]Cl 在 H₂ 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到tetrakis(trimethyl-l5-phosphaneyl)iridium(VII) chloride dihydride
  参考文献：
  名称：

  Thorn, David L.; Tulip, Organometallics, 1982, vol. 1, # 12, p. 1580 - 1586

  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.
• Aqueous Organometallic Chemistry of <i>mer</i>-Ir(H)₂(PMe₃)₃X Complexes
  作者：Joseph S. Merola、Trang Le Husebo、Kelly E. Matthews

  DOI：10.1021/om300140f

  日期：2012.5.28

  A series of Ir(H)(2)(PMe3)(3)X compounds where X = various anionic ligancls has been synthesized. The most studied of this group with X = Cl has been characterized fully, including by X-ray crystallography. For X = Cl, PhCO2-, dissolution in water results in the establishment of the equilibrium Ir(H)(2)(PMe3)(3)X + H2O = [Ir(H)(2)(PMe3)(3)(H2O)]X-+(-), which is responsible for the reaction of these compounds with unsaturated organic compounds. Reactions between the dihydrides and alkynes in water as well as the thermodynamics of the aqueous equilibrium are discussed.