Quantitative investigation of bonding characteristics in ternary Zintl anions: Charge and energy analysis of [Sn2E152(ZnPh)]− (E15 = Sb, Bi) and [Sn2Sb5(ZnPh)2]3−
Quantitative investigation of bonding characteristics in ternary Zintl anions: Charge and energy analysis of [Sn2E152(ZnPh)]− (E15 = Sb, Bi) and [Sn2Sb5(ZnPh)2]3−
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三元 Zintl 阴离子键合特性的定量研究：[Sn2E152(ZnPh)]â (E15â=âSb, Bi) 和 [Sn2Sb5(ZnPh)2]3â 的电荷和能量分析
DOI：
10.1002/jcc.23560
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发表时间：
2014
影响因子：
3
通讯作者：
R. Tonner
中科院分区：
文献类型：
--
作者：
M. Raupach;S. Dehnen;R. Tonner
锌离子及其配合物的化学键分析主要是基于前沿分子轨道（FMO）分析。虽然这种方法提供了非凡的见解，但它无法为这些化合物中的化学键提供定量测量。本文用电荷和能量分析方法研究了有机锌偶联锌阴离子[Sn2E152(ZnPh)]−(E15= Sb, Bi)和[Sn2Sb5(ZnPh)2]3‐。部分电荷分析证实了自然居群分析法比Hirshfeld法更可靠地计算了Zintl阴离子的扩散电荷密度。在接下来的步骤中，使用结合化学价轨道的能量分解分析方法，对有机锌碎片与Zintl阴离子笼之间的化学键进行定量分析。从这个分析中，我们得出结论，共用电子描述更合适地代表了这些化合物中的化学键。该键的特点是向ZnPh片段极化的σ -型键和向锌的p -轨道强的π -给能（轨道相互作用的15-20%）。静电作用在FMO分析中没有被考虑，但它占了吸引金属-配体相互作用的三分之二左右，在讨论这些化合物的化学键时不应忽视它。因此，使用具有更好的σ -或π -接受能力的配体可能有助于在未来进一步稳定具有多Zintl阴离子的有趣类化合物。©2014 Wiley期刊公司
The analysis of chemical bonding in Zintl anions and complexes thereof is mostly based on frontier molecular orbital (FMO) analysis. While this approach delivers remarkable insights, it falls short of providing quantitative measures for chemical bonding in these compounds. Here, we investigate the organozinc‐ligated Zintl anions [Sn2E152(ZnPh)]−(E15= Sb, Bi) and [Sn2Sb5(ZnPh)2]3‐with charge and energy analysis methods. Partial charge analysis confirms that natural population analysis is more reliable than the Hirshfeld method for the diffuse charge density of the Zintl anions. In a subsequent step, the combined method energy decomposition analysis with natural orbitals for chemical valence is used to deliver quantitative results for the chemical bond between the organozinc fragment and the Zintl anionic cage. From this analysis, we conclude that the shared‐electron description represents the chemical bonding in these compounds more appropriate. The bonding is characterized by a σ‐type bond polarized toward the ZnPh fragment and a strong π‐donation (15–20% of orbital interaction) into the p‐orbitals at zinc. Electrostatic contributions, which are not considered in FMO analyses, make up around two‐thirds of the attractive metal–ligand interaction and should not be neglected in the discussion of chemical bonding in these compounds. Usage of ligands with better σ‐ or π‐accepting ability might thus serve to further stabilize the interesting class of compounds with multinary Zintl anions in the future. © 2014 Wiley Periodicals, Inc.