de Azevedo Santos Lucas, Hamlin Trevor A, Ramalho Teodorico C, Bickelhaupt F Matthias
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Department of Chemistry, Institute of Natural Sciences, Universidade Federal de Lavras, 37200-900, Lavras, MG, Brazil and Center for Basic and Applied Research, University Hradec Kralove, Hradec Kralove, Czech Republic.
Phys Chem Chem Phys. 2021 Jun 30;23(25):13842-13852. doi: 10.1039/d1cp01571k.
We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3PnA- (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A- and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.
我们使用ZORA-M06/QZ4P水平的最新相对论密度泛函计算方法，分析了典型的氮族元素键合模型复合物D3PnA-（Pn = N、P、As、Sb；D、A = F、Cl、Br）的结构和稳定性。我们完成了两项任务：（i）基于一组一致的数据计算氮族元素键强度的准确趋势；（ii）结合定量的Kohn-Sham分子轨道（KS-MO）理论、规范能量分解分析（EDA）和电荷分布的Voronoi变形密度（VDD）分析，通过对键合机制的详细分析，使这些趋势合理化。我们发现，氮族元素键具有显著的共价特征，这源于A-的孤对电子与D3Pn的σ*之间强烈的HOMO-LUMO相互作用。因此，氮族元素键的潜在机制与氢键、卤键和硫族元素键的机制相似。
