fac-H2IrCl(P(CH3)3)3 | 150938-92-4

• 英文名称: fac-H2IrCl(P(CH3)3)3
• CAS: 150938-92-4；472987-25-0
• 化学式: C₉H₂₉ClIrP₃
• 分子量: 457.924
• InChiKey: BHKWKSYTMJKJNU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 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：

  fac-H2IrCl(P(CH3)3)3 以 苯 为溶剂， 以0%的产率得到mer-cis-H2IrCl(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：

  [Ir(PMe3)3Cl(η(2)-cyclooctene)] 、 氢气 以 苯 为溶剂， 以99%的产率得到fac-H2IrCl(P(CH3)3)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

文献信息

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

  DOI：——

  日期：——
• 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.
• Le, Trang X.; Merola, Joseph S., Organometallics, 1993, vol. 12, # 10, p. 3798 - 3799
  作者：Le, Trang X.、Merola, Joseph S.

  DOI：——

  日期：——
• Dinuclear iridium complexes with unsupported Ir–Cl–Ir bridges
  作者：Joseph S. Merola、Trang Le Husebo、Henry E. Selnau

  DOI：10.1016/j.ica.2012.04.014

  日期：2012.7

  Two unusual dinuclear iridium complexes are reported with unsupported bridging chloride ligands. The first comes from an aqueous solution of H2ClIr(PMe3)(3) by the addition of KPF6.[GRAPHICS].The second is formed in the reaction between H(C6H5)ClIr(PMe3)(3) and TlPF6 in dichloromethane.[GRAPHICS].Single crystal X-ray structures are provided for both mu-chlorodiiridium complexes. (C) 2012 Elsevier B.V. All rights reserved.
• An unusual trimerization reaction of an alkyne on iridium
  作者：Trang X. Le、Henry E. Selnau、Joseph S. Merola

  DOI：10.1016/0022-328x(94)80058-8

  日期：1994.4

  Reactions between mer-(Me3P)3Ir(H)(H)(Cl) and 2-ethynylpyridine in water or mer-(Me3P)3Ir(H)(Ph)(Cl) and 2-ethynylpyridine and Tl[PF6] in CH2Cl2 both lead to the formation of an unusual 3.3.0-azairidabicyclooctatriene, 3. Complex 3 was characterized by single crystal X-ray diffraction and was found to crystallize in the triclinic space group P1BAR with a = 12.060(3) angstrom, b = 12.512(3) angstrom, c = 14.833(3) angstrom, alpha = 87.25(2)degrees, beta = 73.21(2), gamma = 69.93(2)degrees and V = 2009.4(9) angstrom3 for Z = 2. Complex 3 appears to form via a[GRAPHICS]3, P = PMe; py = pyridyl sequence of reactions involving (i) coupling of two equivalents of 2-ethynylpyridine at iridium (I) to yield a metallacylopentadiene complex; (ii) addition of a third equivalent of 2-ethynylpyridine; (iii) rearrangement of the third equivalent of 2-ethynylpyridine to a vinylidene; and (iv) nucleophilic attack of a pendant pyridine on the a carbon of the vinylidene.