Pentavalent pnictogen bonds involving triarylpnictogen catecholates as strong Lewis acids: Crystallographic survey and theoretical analysis

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-03-07 DOI:10.1016/j.comptc.2025.115171

Ruotong Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu

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Abstract

As a novel class of Lewis acids, triarylpnictogen(V) catecholate compounds have attracted increasing attention in anion binding and transport, supramolecular chemistry, and organocatalysis. In this work, pentavalent pnictogen bonds (PnBs) formed by these compounds and chloride ion were investigated in detail via the combination of crystallographic data analysis and quantum chemical calculations. Owing to the much shorter intermolecular distances and the considerably more negative binding energies, pentavalent PnBs show a remarkably enhanced strength compared with conventional trivalent PnBs, leading to a greater degree of covalency for hypervalent PnBs. Energy decomposition analysis revealed that both the electrostatic and the orbital terms contribute significantly to the attraction of pentavalent PnBs, while the Pauli repulsion term plays an important role in rationalizing the observed Lewis acidic tendency of pnictogens. In addition, the influence of different substituents either in the phenyl rings or in the catecholate group was also examined for these interactions.

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.