Assessing the catalytic potential of novel halogen substituted carbene NHC (F, Cl, Br, I) catalysts in [3 + 2] cycloaddition reactions: A computational investigation

This study investigated the catalytic behavior of NHC-X ligands (X = F, Cl, Br, I) in cycloaddition reactions, focusing on both mononuclear and binuclear pathways. Using NCI (noncovalent interaction), RDG (reduced density gradient), ELF (electron localization function), and LOL (localized orbital lo...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2024-10, Vol.53 (4), p.16635-16646
Main Authors: Khairbek, Ali A, Badawi, Mohammad Abd-Al Hakim, Alzahrani, Abdullah Y, Thomas, Renjith
Format: Article
Language:English
Subjects:
Acetonitrile
Catalysts
Cycloaddition
Energy value
Gibbs free energy
Ligands
Orbital stability
Solvent effect
Solvents
Steric hindrance
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Summary:This study investigated the catalytic behavior of NHC-X ligands (X = F, Cl, Br, I) in cycloaddition reactions, focusing on both mononuclear and binuclear pathways. Using NCI (noncovalent interaction), RDG (reduced density gradient), ELF (electron localization function), and LOL (localized orbital locus) computational analyses, the electronic interactions and stability of the ligands were examined. The results showed that NHC-Cl exhibited the least steric hindrance and strongest transition state stabilization, making it the most efficient catalyst. NHC-F also demonstrated strong stabilization, particularly in the binuclear pathway. In contrast, NHC-Br showed moderate efficiency, whereas NHC-I was the least effective owing to higher Gibbs free energy values and greater steric hindrance, especially in polar solvents such as water and acetonitrile. This study emphasizes the crucial role of solvent effects and thermodynamic factors in influencing the catalytic efficiency. These findings provide a framework for optimizing NHC-based catalysts for chemical transformations. This study investigated the catalytic behavior of NHC-X ligands (X = F, Cl, Br, I) in cycloaddition reactions, focusing on both mononuclear and binuclear pathways.
ISSN:1477-9226
1477-9234
DOI:10.1039/d4dt02225d