monozirconium(III) dihydride | 123825-87-6

• 英文名称: monozirconium(III) dihydride
• CAS: 123825-87-6
• 化学式: H₂Zr
• 分子量: 93.2399
• InChiKey: OFSNIQFFJIIEEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.54
• 重原子数：
  1.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  氟化锆 、 氢气 以 neat (no solvent, gas phase) 为溶剂， 生成 、 、 、 、 monozirconium(III) dihydride
  参考文献：
  名称：

  Mechanistic and Energetic Details of Adduct Formation and σ-Bond Activation in Zr⁺(H₂)_n Clusters

  摘要：

  The formation of Zr+(H-2)(n) clusters (n = 1-7) has been studied both experimentally and theoretically. Binding energies were determined via temperature-dependent equilibrium measurements, giving -Delta Ho degrees = 14.5 +/- 0.3, 10.7 +/- 0.2, 10.1 +/- 0.3, 9.1 +/- 0.5, 9.2 +/- 0.5, 8.9 +/- 0.6, and 8.5 +/- 0.8 kcal/mol for n = 1-7, respectively. Both DFT(B3LYP) and MP2 calculations gave binding energies in excellent agreement with experiment. Zr+ appears to insert into the first H-2 to form the dihydride as predicted by theory. The rate of insertion was observed to have a negative temperature dependence and a positive pressure dependence, suggesting a cluster-assisted insertion mechanism. Interestingly, both DFT and MP2 calculations suggest that the dihydride may "uninsert" to form a pure dihydrogen cluster with n between 5 and 7.

  DOI：

  10.1021/jp003035u