Computationally rational design of metal-involving halogen bonds with π-covalency: Structures and bonding analysis,Journal of Computational Chemistry

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Computationally rational design of metal-involving halogen bonds with π-covalency: Structures and bonding analysis
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-11-15 , DOI: 10.1002/jcc.27036
Congcong Zhang ₁ , Han Bai ₁ , Junyuan Hu ₁ , Kai Guo ₂ , Lili Zhao _{1,

3}

Affiliation

Traditional π-covalent interactions have been proved in the non-metal halogen bond adducts formed by chloride and halogenated triphenylamine-based radical cations. In this study, we have rationally designed two metal-involving halogen bond adducts with π-covalency property, such as [L1-Pd···I-PTZ]⁺ (i.e., 1) and [L2-Pd···I-PTZ]⁺ (i.e., 2), in which the square-planar palladium complexes serve as halogen bond acceptor and 3,7-diiodo-10H-phenothiazine radical cation (i.e., [I-PTZ]^•+) acts as halogen bond donor. Noncovalent interaction analysis and quantum theory of atoms in molecules analysis revealed that there are notable halogen bond interactions along the Pd···I direction without genuine chemical bond formed in both designed adducts. Energy decomposition analysis together with natural orbital for chemical valence calculations were performed to gain insight into their bonding nature, which demonstrated the presence of remarkable π-covalent interactions and σ-covalent interactions in both 1 and 2. We therefore proposed a new strategy for building the metal-involving halogen bonds with π-covalency property, which will help the further development of new types of halogen bonds.

中文翻译：

具有 π 共价的含金属卤素键的计算合理设计：结构和键合分析

传统的π-共价相互作用已在由氯化物和卤代三苯胺基自由基阳离子形成的非金属卤素键加合物中得到证明。在本研究中，我们合理设计了两种具有π共价性质的金属参与卤键加合物，如[L1-Pd···I-PTZ] ⁺（即1）和[L2-Pd···I- PTZ] ⁺ (ie, 2), 其中方形平面钯络合物作为卤素键受体和 3,7-diiodo-10H-phenothiazine 自由基阳离子 (ie, [I-PTZ] ^•+) 作为卤键供体。分子分析中的非共价相互作用分析和原子量子理论表明，在两种设计的加合物中，沿Pd···I方向存在显着的卤素键相互作用，而没有形成真正的化学键。进行能量分解分析和用于化学价计算的自然轨道以深入了解它们的键合性质，这表明在 1 和 2 中都存在显着的 π-共价相互作用和 σ-共价相互作用。因此，我们提出了一种新的构建策略含金属的卤素键具有π共价性，有助于新型卤素键的进一步发展。

更新日期：2022-11-15

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