A THEORETICAL CASE STUDY OF SUBSTITUENT EFFECTS AND MICROSOLVATION ON THE BINDING SPECIFICITY OF CROWN ETHERS
A THEORETICAL CASE STUDY OF SUBSTITUENT EFFECTS AND MICROSOLVATION ON THE BINDING SPECIFICITY OF CROWN ETHERS
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取代基效应和微溶剂化对冠醚结合专一性的理论案例研究
DOI：
10.1021/jp971509s
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发表时间：
1997
影响因子：
2.9
通讯作者：
R. Kendall
中科院分区：
文献类型：
--
作者：
D. Feller;M. Thompson;R. Kendall
用HARTREE、−、FOCK和二阶微扰理论计算了一个碱金属阳离子和一个新近合成的18-冠-6衍生物的配合物，该配合物将冠醚大环锁定为类D3d构型。与18-冠-6不同，18-冠-6与K+的结合选择性是Na+的100倍，该衍生物对Na+的选择性为4：1。对一个简单的K+↔Na+阳离子交换反应的计算表明，结合偏好发生了微小的变化，有利于Na+，但理论处理中固有的不确定性使我们很难得出明确的结论。考虑了阳离子/s18-冠-6络合物上的两个微溶剂水以及通过与18-冠-6结合的四个微溶剂水的影响。这项研究中使用的理论水平类似于之前发现的与液态实验数据定性一致的约束性偏好。据我们所知，这项工作涉及几个络合物的800多个基函数，……
Hartree−Fock and second-order perturbation theory calculations were performed on complexes of a single alkali metal cation and a recently synthesized derivative of 18-crown-6 that locks the crown macrocycle into a D3d-like configuration. Unlike 18-crown-6, which binds K+ with a 100-fold selectivity over Na+, the derivative prefers Na+ by a factor of 4:1. Calculations on a simple K+ ↔ Na+ cation exchange reaction indicate a small shift in binding preference in favor of Na+, but the inherent uncertainty in the theoretical treatment makes an unequivocal conclusion difficult. The effects of two microsolvating waters attached to the cation/s18-crown-6 complex and up through four microsolvating waters bound to 18-crown-6 were considered. The levels of theory used in this study were similar to those previously found to yield binding preferences in qualitative agreement with liquid-phase experimental data. To the best of our knowledge, this work, which involved more than 800 basis functions for several complexes,...