Work

The Influence of the Solvation on the Bonding of Molecular Complexes of Diatomic Halogens With Nitrogen‐Containing Donors and Their Stability With Respect to the Heterolytic Halogen‐Halogen Bond Splitting

Year: 2024

Type: article

Abstract: ABSTRACT In the framework of SMD approach a systematic computational study of structural, electronic and thermodynamic properties of molecular complexes of Cl 2 , ICl and I 2 with series of N‐containing Lewis bases in solvents of different polarity was carried out. Results indicate that molecular complexes of Cl 2 with strong and medium‐strong LB undergo spontaneous ionization in the acetonitrile solution. The increase of the solvent polarity can change the nature of interaction in X'XLB systems from molecular X'X ← LB donor‐acceptor complexes to 3‐center 4‐electron bound X'→X + ← LB in solvents of medium polarity and to the contact ion pairs X'→[XLB] + in polar solvents. Thus, the controlled generation of cationic [LB∙X] + species is possible by varying the nature of LB, varying the nature of the solvent, and varying the nature of the halogen X. Molecular Cl 2 has the greatest tendency to form ionic species in polar solvents. Spontaneous ionization of molecular nσ complexes of chlorine with strong LB in medium‐polar solvents (starting from OEt 2 , ε = 4.24) should not be neglected and single point solvation energy computations on gas phase optimized geometries are not reliable for such systems.

Source: Journal of Computational Chemistry

DOI: 10.1002/jcc.27549

Authors: Anna V. Pomogaeva, Anna S. Lisovenko, Alexey Y. Timoshkin

Institution: St Petersburg University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: Saint Petersburg State University, Russian Science Foundation

Award: G1519427068