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银离子的协调化学
Brigitte S Fox1, Martin K Beyer, Vladimir E Bondybey
1Institut für Physikalische und Theoretische Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany.
Journal of the American Chemical Society
|November 7, 2002
概括
银酸 (Ag+) 在不同的溶剂中表现出不同的协调. 这项研究揭示了氨酸和水合银团中的联结物交换反应,突出了影响复杂形成的因素.
科学领域:
- 协调化学 协调化学
- 计算化学计算化学
- 物理化学 物理化学
背景情况:
- 银离子 (Ag+) 通常在纯溶剂中显示四面体协调.
- 在氨等连接体的存在下,Ag+形成线性复合体,通常归因于sd混合化.
- 了解在混合溶剂系统中控制Ag+协调的因素至关重要.
研究的目的:
- 为了研究氨酸银离子与水的联结体交换反应.
- 为了探索水合银离子与氨的互补反应.
- 阐明控制混合溶剂集群中的银离子协调的因素.
主要方法:
- 福利埃变换离子旋回子共振 (FT-ICR) 质谱法被用于研究集群反应.
- 进行密度函数理论 (DFT) 计算以补充实验发现.
- 研究了Ag+(NH3) n (n=11-23) 与H2O以及Ag+(H2O) n (n=25-45) 与NH3的反应.
主要成果:
- 连接物交换反应导致具有有限数量的氨连接物的集群.
- 氨酸银集群迅速失去连接体,直到剩下两个或三个NH3,额外的连接体的损失较慢.
- 化银集群迅速吸收多达五个氨基联体,六分之一的吸收效率低下.
结论:
- 竞争效应的微妙平衡控制着银离子协调.
- 关键因素包括Ag+对sd-hybridization的偏好,其对影响键的连接体的极化以及溶剂网络的形成.
- 这些因素共同解释了混合溶剂系统中观察到的协调差异.
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