| 140875-48-5

• CAS: 140875-48-5
• 化学式: C₃₆H₇₀ClIrP₂
• 分子量: 792.572
• InChiKey: RRJYRGDBIINRKQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [(C8H14)2Ir(μ-Cl)]2 、 三环己基膦 在 H₂ 作用下， 以 正戊烷 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  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)

  摘要：

  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-31{H-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.

  DOI：

  10.1021/ic00036a020