Can the solvent enhance the rate of chemical reactions through C-H/π interactions? insights from theory

• Published in: Physical chemistry chemical physics : PCCP 2019-07, Vol.21 (27), p.14821-14831
• Main Authors: Jain, Shailja, Vanka, Kumar
• Format: Article
• Language: English
• Subjects: Carbon; Chemical reactions; Computer simulation; Density functional theory; Free energy; Molecular dynamics; Organic chemistry; Silicon; Solvents; Substrates; Toluene
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c9cp02646k

The current computational study with density functional theory (DFT) shows that the rate of chemical reactions can be influenced through non-covalent C-H/π interactions between substrates and the solvent. It is shown that intramolecular carbon-carbon interaction and CO 2 activation by a low valent silicon complex are both favourably affected by the explicit presence of the solvent toluene, due to C-H/π interactions between toluene and the silicon complex. Furthermore, ab initio molecular dynamics (AIMD) simulations demonstrate that even if the C-H/π interacting solvent molecule is displaced from the complex, another would quickly take its place, thus maintaining the interaction. Hence, the current work shows how non-covalent interactions between solvent and substrate can enhance the rate of the reaction and expands our understanding of the role and influence of the solvent in effecting important chemical transformations. The current computational study with density functional theory (DFT) shows that the explicit presence of C-H/π and π-π interacting solvent molecules is seen to enhance the rate of chemical reactions.