Computational Investigation of Significant Agostic Interactions in Metal-Assisted C-H Cleavage
Location
Science Center: Bent Corridor
Document Type
Poster - Open Access
Start Date
4-28-2023 12:00 PM
End Date
4-28-2023 2:00 PM
Abstract
C-H activation reactions, with their ability to cleave stable carbon hydrogen bonds, has revolutionized the world of synthetic chemistry. Directed C-H activation that can cleave specific C-H bonds have allowed functionalization of these molecules from abundant materials enabling synthesis of complex products. By establishing a better understanding of the mechanism, we can devise better strategies for optimizing these C-H activation reactions. C-H bond cleavage typically constitutes the rate- and selectivity-determining step in C-H activation and can occur through a variety of different mechanisms. In this study, we used density functional theory (DFT) calculations to investigate metal-assisted C-H cleavage with an emphasis on characterizing the agostic complex interaction in this process. While overall mechanism for agostic interactions observed in C-H cleavage processes has been well established, detailed investigation of the mechanism and possible impacts of ligands on these agostic interactions are not well studied. We analyzed Gibbs free energies, Hirshfeld charges, and geometric data to characterize the effects of various ligands on the agostic interaction. Through these studies, we were able to establish a better understanding of the effects of ligands that directly or indirectly participate in the C-H activation process. Moreover, this elucidated possible nuances in the mechanisms which may possibly be applied to improve the efficiency of C-H activation reactions.
Keywords:
C-H activation, Transition metal catalysis, Computational chemistry
Recommended Citation
Nagashima, Kyogo, "Computational Investigation of Significant Agostic Interactions in Metal-Assisted C-H Cleavage" (2023). Research Symposium. 6.
https://digitalcommons.oberlin.edu/researchsymp/2023/posters/6
Major
Chemistry
Project Mentor(s)
Shuming Chen, Chemistry and Biochemistry
2023
Computational Investigation of Significant Agostic Interactions in Metal-Assisted C-H Cleavage
Science Center: Bent Corridor
C-H activation reactions, with their ability to cleave stable carbon hydrogen bonds, has revolutionized the world of synthetic chemistry. Directed C-H activation that can cleave specific C-H bonds have allowed functionalization of these molecules from abundant materials enabling synthesis of complex products. By establishing a better understanding of the mechanism, we can devise better strategies for optimizing these C-H activation reactions. C-H bond cleavage typically constitutes the rate- and selectivity-determining step in C-H activation and can occur through a variety of different mechanisms. In this study, we used density functional theory (DFT) calculations to investigate metal-assisted C-H cleavage with an emphasis on characterizing the agostic complex interaction in this process. While overall mechanism for agostic interactions observed in C-H cleavage processes has been well established, detailed investigation of the mechanism and possible impacts of ligands on these agostic interactions are not well studied. We analyzed Gibbs free energies, Hirshfeld charges, and geometric data to characterize the effects of various ligands on the agostic interaction. Through these studies, we were able to establish a better understanding of the effects of ligands that directly or indirectly participate in the C-H activation process. Moreover, this elucidated possible nuances in the mechanisms which may possibly be applied to improve the efficiency of C-H activation reactions.
