Structures and stability of I2 and ICl complexes with pyridine: Ab initio and DFT study,Journal of Computational Chemistry

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Structures and stability of I2 and ICl complexes with pyridine: Ab initio and DFT study
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-01-02 , DOI: 10.1002/jcc.27300
Anna V Pomogaeva ₁ , Anna S Lisovenko ₁ , Alexey Y Timoshkin ₁

Affiliation

Theoretical investigation of thermodynamic stability and bonding features of possible isomers of the molecular and ionic complexes of pyridine with molecular iodine and iodine monochloride IX (X = I,Cl) is presented. M06-2X DFT functional is found to provide bond distances and dissociation energies which are close to those obtained at high-level ab initio CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz benchmark computations for the most stable isomers, formed via donation of a lone pair of nitrogen atom of pyridine to the iodine atom. These isomers are by 23–33 kJ mol⁻¹ (in case of I₂) and by 39–56 kJ mol⁻¹ (in case of ICl) more stable than other molecular complexes. T-shaped π-σ* bonded isomers turn out to be energetically comparable with van der Waals bound compounds. Among the ionic isomers, structures featuring [IPy₂]⁺ cation with I₃⁻ or ICl₂⁻ counterions are more stable. Oligomerization favors ionic isomers starting from the tetrameric clusters of the composition (IX)₄Py₄.

中文翻译：

I2 和 ICl 与吡啶配合物的结构和稳定性：从头算和 DFT 研究

对吡啶与分子碘和一氯化碘 IX (X = I,Cl) 的分子和离子配合物的可能异构体的热力学稳定性和键合特征进行了理论研究。发现 M06-2X DFT 泛函提供的键距和解离能接近于大多数情况下在高级从头算 CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz 基准计算中获得的值稳定的异构体，通过将吡啶的孤对氮原子提供给碘原子而形成。这些异构体比其他分子复合物稳定 23–33 kJ mol ^-1 （在 I ₂的情况下）和 39–56 kJ mol ^-1 （在 ICl 的情况下）。 T 形 π-σ* 键合异构体在能量上与范德华键合化合物相当。在离子异构体中，以[IPy ₂ ] ⁺阳离子与I ₃ ^-或ICl ₂ ^-抗衡离子为特征的结构更稳定。低聚有利于从组合物(IX) ₄ Py ₄的四聚簇开始的离子异构体。

更新日期：2024-01-02

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