chlorodihydridobis(tri-t-butylphosphine)iridium(III) | 141040-32-6

• 英文名称: chlorodihydridobis(tri-t-butylphosphine)iridium(III)
• CAS: 141040-32-6；58904-22-6
• 化学式: C₂₄H₅₆ClIrP₂
• 分子量: 634.329
• InChiKey: HXBIAYOUVIFTTQ-UHFFFAOYSA-M

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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  chlorodihydridobis(tri-t-butylphosphine)iridium(III) 在 氢气 作用下， 以 异丙醇 、 苯 为溶剂， 以61%的产率得到pentahydridobis(tri-t-butylphosphine)iridium(V)
  参考文献：
  名称：

  氢化铱和四氢硼酸盐与大叔膦配体的配合物

  摘要：

  三氯化铱与丙-2-醇中的PBu t 2 Ph或PBu t 3（L）反应生成五坐标二氢化物[IrClH 2 L 2 ]。配合物[IrClH 2（PBu t 2 Ph）2 ]与碘化钠反应生成[IrH 2 I（PBu t 2 Ph）2 ]或与一氧化碳反应生成[Ir（CO）ClH 2（PBu t 2）Ph ）2 ]。与二氢和丙-2-酸钠一起，[IrClH 2 L 2 ]得到相应的五氢化物[IrH 5 L 2]。的类型的氢化物[的IrCl 3- X ħ X（PRBu吨2）2 ]（一）X = 1，R = Me或（b）X = 2，R =卜吨与钠反应四氢得到配合物的[Ir （BH 4）H 2（PRBu t 2）2 ]。这些是非fluxionbl，并已通过1 H，31 P和11 B nmr光谱表征。络合物[Ir（BD 4）H 2（PBu t 3）2]和[Ir（BD 4）DH（PMeBu t 2）2 ]也通过Li

  DOI：

  10.1039/dt9760002069
• 作为产物：
  描述：

  hydrogen hexachloroiridate hydrate 、 三叔丁基膦 以 水 、 异丙醇 为溶剂， 以28%的产率得到chlorodihydridobis(tri-t-butylphosphine)iridium(III)
  参考文献：
  名称：

  氢化铱和四氢硼酸盐与大叔膦配体的配合物

  摘要：

  三氯化铱与丙-2-醇中的PBu t 2 Ph或PBu t 3（L）反应生成五坐标二氢化物[IrClH 2 L 2 ]。配合物[IrClH 2（PBu t 2 Ph）2 ]与碘化钠反应生成[IrH 2 I（PBu t 2 Ph）2 ]或与一氧化碳反应生成[Ir（CO）ClH 2（PBu t 2）Ph ）2 ]。与二氢和丙-2-酸钠一起，[IrClH 2 L 2 ]得到相应的五氢化物[IrH 5 L 2]。的类型的氢化物[的IrCl 3- X ħ X（PRBu吨2）2 ]（一）X = 1，R = Me或（b）X = 2，R =卜吨与钠反应四氢得到配合物的[Ir （BH 4）H 2（PRBu t 2）2 ]。这些是非fluxionbl，并已通过1 H，31 P和11 B nmr光谱表征。络合物[Ir（BD 4）H 2（PBu t 3）2]和[Ir（BD 4）DH（PMeBu t 2）2 ]也通过Li

  DOI：

  10.1039/dt9760002069

文献信息

• Solid-state and solution dynamics of the reversible loss of hydrogen from the iridium nonclassical polyhydride complexes IrClH2(PR3)2(H2) (R = iso-Pr, Cy, tert-Bu)
  作者：Mario Mediati、Glen N. Tachibana、Craig M. Jensen

  DOI：10.1021/ic00036a020

  日期：1992.5

  The complexes IrClH2(PR3)2(H2) (R = Pr(i) (1a), Cy (1b)) were generated through the reaction of the corresponding unsaturated dihydride complexes, IrClH2(PR3)2 (R = Pr(i) (2a), Cy (2b)), with H-2 in solution or the solid state. The complexes were also prepared through treatment of THF solutions of IrCl3.3H2O and 2 equiv of phosphine with 2 equiv of sodium naphthalide under an atmosphere of hydrogen. The molecular structure of 1a.C10H8 was determined by a single-crystal X-ray diffraction study. Crystallographic data for 1a.C10H8: triclinic P1BAR, Z = 2, a = 8.069 (3) angstrom, b = 13.822 (6) angstrom, c = 14.519 (5) angstrom, alpha = 82.56 (3)-degrees, beta = 82.34 (3)-degrees, gamma = 72.90 (3)-degrees, V = 5170 (5) angstrom3; rho(calcd) = 1.737 g/cm3. Under an atmosphere of argon, 1a and 1b eliminate H-2 and convert back to the unsaturated complexes. Variable-temperature H-1 NMR studies of 1a and 1b in toluene-d8 solution under 0.5 atm of H-2 show that they establish rapid equilibria with 2a and 2b, respectively, which are sensitive to hydrogen pressure and temperature. Similar studies of the more sterically hindered IrClH2(PBu(t)3)2 (2c) under 0.5 atm of H-2 show only indirect evidence of a much slower equilibrium with 1c, while low concentrations of 1c can be directly observed under 1 atm of H-2. The presence of dihydrogen ligands in 1a and 1b are indicated by their extremely facile exchange with free H-2 and by the respective minimum T1 values for the H-1 NMR resonance due to the exchanging metal-bound hydrogens at 300 MHz of 22 and 27 ms, respectively. Variable-temperature P-31H-1} NMR spectra of 1a dissolved in toluene-d8 also demonstrate the interconversion of 1a and 2a. The metal bound hydrogens of 1a and 1b undergo D/H exchange in toluene-d8, THF-d8, and CD2Cl2 solutions. The reversible uptake of hydrogen by 2a in the solid state was studied through monitoring of M-H absorptions by FTIR spectroscopy. Comparison of the relative intensities of the M-H infrared absorptions of 1a and 2a with those observed for 1b and 2b in equilibrated samples under 1 atm of H-2 indicates that the equilibrium position lies much more toward the dihydrogen complex in the case of the PPR(i)3 derivative. Similar studies of the reaction of 2a with D2 establish that the intramolecular exchange between the dihydrogen and hydride ligands of 1a occurs in the solid state.