Structures and stability of I2 and ICl complexes with pyridine Ab initio and DFT study

Structures and stability of I2 and ICl complexes with pyridine : Ab initio and DFT study

© 2024 Wiley Periodicals LLC.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 45(2024), 12 vom: 05. März, Seite 903-914
1. Verfasser: Pomogaeva, Anna V (VerfasserIn)
Weitere Verfasser: Lisovenko, Anna S, Timoshkin, Alexey Y
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2024
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article chemical bond iodine iodine chloride isomers molecular complexes pyridine
Beschreibung
Zusammenfassung:© 2024 Wiley Periodicals LLC.
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
Beschreibung:Date Revised 21.03.2024
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X
DOI:10.1002/jcc.27300