鲁 (II) 化物复合物的热力学和动力学水性
Yasuo Matsubara1, Etsuko Fujita, Mark D Doherty
1Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, United States.
这项研究量化了在乙基中化复合物的水性,揭示了与水相比的压缩范围. 这些发现对于催化和太阳能储能应用至关重要.
科学领域:
- 有机金属化学 有机金属化学
- 电化学 电化学 电化学
- 摄影化学的使用
背景情况:
- 过渡金属化物的水性对于催化和太阳能储存至关重要.
- 现有的水性数据是有限的,特别是对于水性溶剂,阻碍了比较.
- 化复合物为研究溶剂对水性影响提供了一个模型系统.
研究的目的:
- 为了确定在乙中化复合物的水性值.
- 为了将这些值与以前在水中报告的值进行比较.
- 了解溶剂对这些复合物的水性范围的影响.
主要方法:
- 热力学循环涉及酸度和电化学电位测量[Ru(η(6) -C6Me6) ((bpy) H]+的热力学周期.
- 使用有机受体的化物转移反应和1H NMR光谱对[Ru(tpy) ((bpy) H]+进行1H NMR光谱.
- 紫外线视光谱学和DFT电子结构计算来描述复杂物.
主要成果:
- 估计的乙二烯含水量:54 ± 2 kcal/mol为[Ru((η(6) -C6Me6) ((bpy) H]+和39 ± 3 kcal/mol为[Ru(tpy) ((bpy) H]+.
- 水中的相应值分别为31和22kcal/mol.
- 在乙二中估计的pKa值为22.5±0.1的[Ru((η(6) -C6Me6) ((bpy) H]+和32±3的[Ru(tpy) ((bpy) H]+.
结论:
- 溶剂从酸转移到水中压缩了化复合物的水性范围.
- 确定了带有减少bpy和tpy连接体的鲁复合体.
- 该研究提供了不同溶剂中水性度的基本比较数据.
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