Trends in the stability of covalent dative bonds with variable solvent polarity depend on the charge transfer in the Lewis electron-pair system

In general, the stability of neutral complexes with dative bonds increases as the polarity of the solvent increases. This is based on the fact that the dipole moment of the complex increases as the charge transferred from the donor to the acceptor increases. As a result, the solvation energy of the...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2023-10, Vol.25 (38), p.25961-25964
Main Authors: Lo, Rabindranath, Manna, Debashree, Miriyala, Vijay Madhav, Nachtigallová, Dana, Hobza, Pavel
Format: Article
Language:English
Subjects:
Charge transfer
Dipole moments
Molecular dynamics
Polarity
Solvation
Solvents
Stability
Subsystems
Trends
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Summary:In general, the stability of neutral complexes with dative bonds increases as the polarity of the solvent increases. This is based on the fact that the dipole moment of the complex increases as the charge transferred from the donor to the acceptor increases. As a result, the solvation energy of the complex becomes greater than that of subsystems, causing an increase in the stabilization energy with increasing solvent polarity. Our research confirms this assumption, but only when the charge transfer is sufficiently large. If it is below a certain threshold, the increase in the complex's dipole moment is insufficient to result in a higher solvation energy than subsystems. Thus, the magnitude of the charge transfer in the Lewis electron-pair system determines the stability trends of dative bonds with varying solvent polarity. We used molecular dynamics (MD) simulations based on an explicit solvent model, which is considered more reliable, to verify the results obtained with a continuous solvent model. Depending upon the extent of charge transfer between the subsystems, the neutral dative bond complexes may stabilise or destabilise with increase in solvent polarity.
ISSN:1463-9076
1463-9084
DOI:10.1039/d3cp03445c