σ-Donation and π-Backdonation Effects in Dative Bonds of Main-Group Elements
σ-Donation and π-Backdonation Effects in Dative Bonds of Main-Group Elements
复制标题
主族元素配位键中的α-捐赠和β-回赠效应
DOI：
10.1021/acs.jpca.1c05956
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Vogiatzis, Konstantinos D.
中科院分区：
文献类型：
--
作者：
Smith, Brett A.;Vogiatzis, Konstantinos D.
供体-受体相互作用的性质对于理解结合键是很重要的，并且可以为许多化学过程提供重要的见解。在这里，我们进行了一项计算研究，以阐明不同类型的加法相互作用之间的实质性差异。为此，我们开发了一个由20个由共轭键稳定的分子配合物组成的数据集（DAT20）。一项基准研究考虑了许多流行的密度函数与精确量子化学相互作用能和几何形状的关系，揭示了DAT20配合物之间的两种不同趋势。通过前沿分子轨道、扩展过渡态化学价态自然轨道（ETS-NOCV）和自然能量分解分析（NEDA）进一步探讨了这种行为。这些方法揭示了供体和受体分子之间的正向和反向给予的程度，以及它们如何影响总相互作用能和分子几何形状。提出了一种新的键的分类方法。
The nature of donor–acceptor interactions is important for the understanding of dative bonding and can provide vital insights into many chemical processes. Here, we have performed a computational study to elucidate substantial differences between different types of dative interactions. For this purpose, a data set of 20 molecular complexes stabilized by dative bonds was developed (DAT20). A benchmark study that considers many popular density functionals with respect to accurate quantum chemical interaction energies and geometries revealed two different trends between the complexes of DAT20. This behavior was further explored by means of frontier molecular orbitals, extended-transition-state natural orbitals for chemical valence (ETS-NOCV), and natural energy decomposition analysis (NEDA). These methods revealed the extent of the forward and backdonation between the donor and acceptor molecules and how they influence the total interaction energies and molecular geometries. A new classification of dative bonds is suggested.