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金属与pi-和sigma-模式的...pi(arene) 相互作用的分子结构

Georgy K Fukin¹, Sergey V Lindeman, Jay K Kochi

¹Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA.

Journal of the American Chemical Society

|July 11, 2002

概括

大的金属酸,鲁比 (Rb+) 和 (Cs+),与六基替代的二烯形成强烈的二烯相互作用. (K+) 也相互作用,但 (Na+) 则没有,显示出依赖大小的结合连续性.

科学领域:

无机化学无机化学
超分子化学超分子化学
物理有机化学有机化学

背景情况:

单价金属酸 (Na+,K+,Rb+,Cs+) 是由静电和溶解力控制的简单充电球体.
在各种化学和生物系统中,阴离子 () 相互作用至关重要.
了解与芳香系统的阳离子相互作用是设计新材料和催化剂的关键.

研究的目的:

为了研究子π(烯) 的金属子 (Na +,K +,Rb +,Cs +) 与六基替代衍生物的相互作用.
根据离子体大小阐明这些相互作用的结合模式和强度.
将这些发现整合到电友相互作用与的更广泛背景中.

主要方法:

使用计算建模来研究金属酸和六基替代 (C6E6,其中E=甲氧甲基) 之间的相互作用.
分析的重点是生成的复合体的几何和电子结构.
结合方式 (例如,n1结合,n2结合) 和相互作用强度的比较.

主要成果:

卢比 (Rb+) 和 (Cs+) 离子与 η1 结合 (西格玛-烯复合体) 形成强烈的离子π () 相互作用.
(K+) 离子表现出类似的相互作用,但与η2结合 (pi-arene复合物),类似于银 (I) /arene复合物.
在相同的条件下, (Na+) 阴离子没有显著的阴离子π(烯) 相互作用.

结论:

金属π(烯) 相互作用强烈依赖于子大小,较大的子 (Rb+, Cs+) 形成更强的键.
观察到的结合模式 (η1 vs. η2) 代表了西格玛-皮结合的连续性,扩展了穆利肯的电荷转移理论.
这些发现提供了对非共价相互作用及其在分子识别和自我组装中的作用的基本见解.

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