Cooperativity and halonium transfer in the ternary NCI···CH3I···−CN halogen-bonded complex: An ab initio gas phase study

IF 2.1 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY
Rubén D. Parra
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Abstract

Context

The strength and nature of the two halogen bonds in the NCI···CH3I···CN halogen-bonded ternary complex are studied in the gas phase via ab initio calculations. Different indicators of halogen bond strength were employed to examine the interactions including geometries, complexation energies, Natural Bond Order (NBO) Wiberg bond indices, and Atoms in Molecules (AIM)-based charge density topological properties. The results show that the halogen bond is strong and partly covalent in nature when CH3I donates the halogen bond, but weak and noncovalent in nature when CH3I accepts the halogen bond. Significant halogen bond cooperativity emerges in the ternary complex relative to the corresponding heterodimer complexes, NCI···CH3I and CH3I···CN, respectively. For example, the CCSD(T) complexation energy of the ternary complex (-18.27 kcal/mol) is about twice the sum of the complexation energies of the component dimers (-9.54 kcal/mol). The halonium transfer reaction that converts the ternary complex into an equivalent one was also investigated. The electronic barrier for the halonium transfer was calculated to be 6.70 kcal/mol at the CCSD(T) level. Although the MP2 level underestimates and the MP3 overestimates the barrier, their calculated MP2.5 average barrier (6.44 kcal/mol) is close to that of the more robust CCSD(T) level. Insights on the halonium ion transfer reaction was obtained by examining the reaction energy and force profiles along the intrinsic reaction coordinate, IRC. The corresponding evolution of other properties such as bond lengths, Wiberg bond indices, and Mulliken charges provides specific insight on the extent of structural rearrangements and electronic redistribution throughout the entire IRC space.

Methods

The MP2 method was used for geometry optimizations. Energy calculations were performed using the CCSD(T) method. The aug-cc-pVTZ basis set was employed for all atoms other than iodine for which the aug-cc-pVTZ-PP basis set was used instead.

三元 NCI-CH3I----CN 卤键络合物中的合作性和卤素转移:一项ab initio气相研究。
背景:通过 ab initio 计算研究了 NCI-CH3I----CN 卤键三元络合物中两个卤键在气相中的强度和性质。研究采用了卤素键强度的不同指标来考察相互作用,包括几何形状、络合能、自然键序(NBO)维伯格键指数以及基于原子分子(AIM)的电荷密度拓扑特性。结果表明,当 CH3I 捐献卤素键时,卤素键是强共价键,而当 CH3I 接受卤素键时,卤素键是弱共价键。相对于相应的异二聚体复合物 NCI-CH3I 和 CH3I----CN 而言,三元复合物中出现了显著的卤键合作性。例如,三元复合物的 CCSD(T) 络合能(-18.27 kcal/mol)大约是二聚体组分络合能总和(-9.54 kcal/mol)的两倍。我们还研究了将三元复合物转化为等价复合物的卤鎓转移反应。在 CCSD(T) 水平上计算出的卤鎓转移电子势垒为 6.70 kcal/mol。虽然 MP2 水平低估了电子势垒,而 MP3 水平高估了电子势垒,但他们计算出的 MP2.5 平均电子势垒(6.44 kcal/mol)接近更稳健的 CCSD(T) 水平。通过研究沿固有反应坐标(IRC)的反应能量和作用力曲线,获得了对卤离子转移反应的深入了解。其他性质(如键长、维伯格键指数和穆利肯电荷)的相应演变提供了关于整个 IRC 空间中结构重排和电子再分布程度的具体见解:采用 MP2 方法进行几何优化。能量计算采用 CCSD(T) 方法。除碘以外的所有原子都使用了 aug-cc-pVTZ 基础集,而碘则使用了 aug-cc-pVTZ-PP 基础集。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Journal of Molecular Modeling
Journal of Molecular Modeling 化学-化学综合
CiteScore
3.50
自引率
4.50%
发文量
362
审稿时长
2.9 months
期刊介绍: The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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