Tuning the metal–ligand bond in the σ-complexes of stannylenes and azabenzenes,Journal of Computational Chemistry

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Tuning the metal–ligand bond in the σ-complexes of stannylenes and azabenzenes
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2021-08-21 , DOI: 10.1002/jcc.26741
Barbara Bankiewicz ₁ , Stephan Kupfer ₂ , Piotr Matczak ₃

Affiliation

The metal–ligand bond in a set of 60 σ-complexes has been investigated by electronic structure computations. These σ-complexes originate from the unique combination of 12 stannylenes (SnX₂) with five azabenzene ligands (pyridine, pyrazine, pyrimidine, pyridazine, and s-triazine), where the nitrogen center of the ligand acts as σ-donor and the tin(II) center as σ-acceptor in a 1:1 fashion. The Sn ← N bond and the total interaction between the stannylene and azabenzene moieties of the σ-complexes are characterized in depth to relate the Sn ← N strength to the substitution pattern at SnX₂ and to the number and the positioning of N atoms in the azabenzenes. Such X substituents as (iso)cyano and trifluoromethyl groups enhance the interaction strength, while the presence of alkyl, phenyl, and silyl substituents in SnX₂ diminishes the stability of σ-complexes. A gradual weakening of the total interaction is associated with the growing number of N atoms in the azabenzenes, while the N-atom positioning in pyridazine is particularly effective in strengthening the interaction with stannylenes. Variations in the Sn ← N bond strength usually follow those in the total interaction between the moieties but the interacting quantum atoms picture of Sn ← N reveals certain intriguing exceptions.

中文翻译：

调节亚锡苯和氮杂苯的 σ 配合物中的金属-配体键

已经通过电子结构计算研究了一组 60 个σ复合物中的金属 - 配体键。这些σ 配合物源自 12 个亚锡 (SnX ₂ ) 与五个氮杂苯配体（吡啶、吡嗪、嘧啶、哒嗪和 s-三嗪）的独特组合，其中配体的氮中心作为σ供体和锡(II)以 1:1 的方式以σ受体为中心。Sn ← N 键以及σ配合物的亚锡基和氮杂苯部分之间的总相互作用被深度表征，以将 Sn ← N 强度与 SnX ₂处的取代模式相关联以及氮杂苯中 N 原子的数量和位置。(异)氰基和三氟甲基等X取代基增强了相互作用强度，而SnX ₂中烷基、苯基和甲硅烷基取代基的存在降低了σ-配合物的稳定性。总相互作用的逐渐减弱与氮杂苯中 N 原子数量的增加有关，而哒嗪中的 N 原子位置在加强与亚锡苯的相互作用方面特别有效。Sn ← N 键强度的变化通常遵循部分之间总相互作用的变化，但 Sn ← N 的相互作用量子原子图片揭示了某些有趣的例外。

更新日期：2021-09-24

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