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气友性相互作用是否与键相竞争? 基于初步计算的实验证据和合理化
Antonio Codina1, Eduardo J Fernández, Peter G Jones
1Departamento de Química, Universidad de La Rioja Grupo de Síntesis Química de La Rioja, UA-CSIC, Madre de Dios 51, E-26004 Logroño, Spain.
Journal of the American Chemical Society
|June 6, 2002
概括
银和黄金复合体表现出独特的结构安排,由金属对金属相互作用和键驱动. 理论计算显示,金金相互作用比银银更强,影响分子结构.
科学领域:
- 协调化学 协调化学
- 超分子化学 超分子化学
- 计算化学计算化学
背景情况:
- 金属与金属的相互作用和结合对于决定协调复合物的固态结构至关重要.
- 了解这些非共价相互作用是设计具有特定性质的新材料的关键.
研究的目的:
- 合成和表征含有化烯联体的银 (I) 和金 (I) 复合物.
- 研究这些复合体中金属与金属相互作用和键之间的相互作用.
- 通过ab initio计算理论分析这些相互作用的强度和性质.
主要方法:
- 银 (I) 和金 (I) 复合物的合成和单晶X射线衍射分析.
- 在模型系统上进行初始计算 (HF和MP2级),以研究Ag (I) -Ag (I),Au (I) -Au (I) 和N-H...F的键相互作用.
主要成果:
- 银复合体1显示了一个梯子类型的结构,具有Ag(I) -Ag(I) 相互作用和N-H...F键.
- 金复合物2形成了离散的二次体,具有Au(I) -Au(I) 相互作用和N-H...F键.
- 理论计算表明Au (I) -Au (I) 相互作用比Ag (I) -Ag (I) 相互作用更强.
- 在黄金复合体中,N-H...F结和Au (I) -Au (I) 接触的强度是可以比较的.
结论:
- 金复合体中的金属与金属相互作用和键的共存和可比强度导致竞争和多样化的结构安排.
- 这些发现提供了对金属复合体在固态中自我组装的因素的见解.
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