Interplay between chalcogen bonds and dynamic covalent bonds,Organic Chemistry Frontiers

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Interplay between chalcogen bonds and dynamic covalent bonds
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2022-05-27 , DOI: 10.1039/d2qo00684g
Shuaipeng Jia _{1,

2} , Hebo Ye ₁ , Lei You _{1,

2,

3}

Affiliation

Chalcogen bonds as a type of supramolecular interactions have been attracting increasing attention, and studies on their regulating mechanisms are of importance. Herein, we demonstrate the interplay between chalcogen bonds and dynamic covalent chemistry (DCC) toward the investigation of chalcogen bonding and control over imine systems. The intramolecular Chal⋯O/N chalcogen bonding was revealed to modulate the conformational preference of ortho-chalcogen benzaldehydes and associated imines. The role of chalcogen bond in shifting dynamic imine exchange was systematically studied, with chalcogen bonding significantly decelerating the kinetics, while thermodynamically stabilizing the imines. Computational studies further unraveled mechanistic insights for chalcogen bonding, with orbital and electrostatic interactions accounting for the major contribution. Moreover, orbital interaction mainly makes up the difference from S to Te, and tellurium enables the strongest interaction, in line with the largest effect of Te on the movement of the imine exchange equilibrium. By utilizing the effects of chalcogen bonds on imine DCC, the reversal of the thermodynamic and kinetic selectivity of dynamic covalent systems was controlled. The results should open up opportunities for molecular recognition, dynamic assemblies, catalysis, and associated endeavors.

中文翻译：

硫属元素键和动态共价键之间的相互作用

硫属元素键作为一种超分子相互作用受到越来越多的关注，对其调控机制的研究具有重要意义。在此，我们展示了硫属元素键和动态共价化学 (DCC) 之间的相互作用，以研究硫属元素键合和对亚胺系统的控制。揭示了分子内 Chal⋯O/N 硫属元素键可调节邻位的构象偏好-硫属元素苯甲醛和相关的亚胺。系统地研究了硫族键在转移动态亚胺交换中的作用，硫族键显着降低了动力学，同时在热力学上稳定了亚胺。计算研究进一步揭示了硫属元素键合的机理见解，其中轨道和静电相互作用是主要贡献。此外，轨道相互作用主要弥补了从 S 到 Te 的差异，而碲的相互作用最强，这与 Te 对亚胺交换平衡运动的最大影响一致。通过利用硫属元素键对亚胺 DCC 的影响，控制了动态共价体系的热力学和动力学选择性的逆转。结果应该为分子识别开辟机会，

更新日期：2022-05-27

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