水合金属离子的水交换速率

25 °C 下单个配位水分子的一级交换速率常数(¹⁷O NMR),由它算出的半衰期与艾林活化自由能,以及八面体 → 四方锥的配体场活化能。

14 行
[Cu(HX2O)X6]X2+\ce{[Cu(H2O)6]^2+}d⁹5.7 × 10⁹1.2 × 10⁻¹⁰17.3−0.07Helm & Merbach 2005
[Cr(HX2O)X6]X2+\ce{[Cr(H2O)6]^2+}d⁴1.2 × 10⁸5.8 × 10⁻⁹26.9−0.07Helm & Merbach 2005
[Mn(HX2O)X6]X2+\ce{[Mn(H2O)6]^2+}d⁵2.1 × 10⁷3.3 × 10⁻⁸31.2−0.00Helm & Merbach 2005
[Fe(HX2O)X6]X2+\ce{[Fe(H2O)6]^2+}d⁶4.4 × 10⁶1.6 × 10⁻⁷35.10.07Helm & Merbach 2005
[Co(HX2O)X6]X2+\ce{[Co(H2O)6]^2+}d⁷3.2 × 10⁶2.2 × 10⁻⁷35.90.13Helm & Merbach 2005
[Mg(HX2O)X6]X2+\ce{[Mg(H2O)6]^2+}d⁰5.3 × 10⁵1.3 × 10⁻⁶40.30.00Neely & Connick 1970
[Ti(HX2O)X6]X3+\ce{[Ti(H2O)6]^3+}d¹1.8 × 10⁵3.9 × 10⁻⁶43.00.07Helm & Merbach 2005
[Ni(HX2O)X6]X2+\ce{[Ni(H2O)6]^2+}d⁸320002.2 × 10⁻⁵47.30.20Helm & Merbach 2005
[V(HX2O)X6]X3+\ce{[V(H2O)6]^3+}d²5000.001457.60.13Helm & Merbach 2005
[Fe(HX2O)X6]X3+\ce{[Fe(H2O)6]^3+}d⁵1600.004360.4−0.00Helm & Merbach 2005
[V(HX2O)X6]X2+\ce{[V(H2O)6]^2+}d³870.00862.00.20Helm & Merbach 2005
[Al(HX2O)X6]X3+\ce{[Al(H2O)6]^3+}d⁰1.30.5472.40.00Hugi-Cleary et al. 1985
[Cr(HX2O)X6]X3+\ce{[Cr(H2O)6]^3+}d³2.4 × 10⁻⁶2.9 × 10⁵105.10.20Helm & Merbach 2005
[Ir(HX2O)X6]X3+\ce{[Ir(H2O)6]^3+}d⁶ (LS)1.1 × 10⁻¹⁰6.3 × 10⁹129.90.40Cusanelli et al. 1996

半衰期 = ln 2/k;ΔG‡ 由艾林方程 k = (k_BT/h)e^(−ΔG‡/RT) 算出。配体场活化能用只含 σ 作用的角重叠模型计算(LS 为低自旋),只解释数量级。

数据来源

  1. L. Helm & A. E. Merbach, “Inorganic and bioinorganic solvent exchange mechanisms”, Chem. Rev. 105, 1923–1959 (2005): first transition series.
  2. D. Hugi-Cleary, L. Helm & A. E. Merbach, Helv. Chim. Acta 68, 545–554 (1985): Al³⁺.
  3. J. Neely & R. Connick, J. Am. Chem. Soc. 92, 3476–3478 (1970): Mg²⁺.
  4. A. Cusanelli, U. Frey, D. T. Richens & A. E. Merbach, J. Am. Chem. Soc. 118, 5265–5271 (1996): Ir³⁺.

在这些课程中使用