Abstract
Organometallic reactions are a fundamental class of chemical transformations. The mechanisms of organometallic reactions are routinely modeled by calculating intermediates and transition-state structures on a potential energy surface with density functional theory (DFT). The translation of these calculated structures to a reaction mechanism is typically done under the umbrella of statistical transition state theory. This dissertation reports the use of DFT calculations and quasiclassical direct dynamics trajectories to explore the possibility of nonstatistical dynamic effects in organometallic reactions. Chapter 1 provides a brief review of potential energy surfaces, transition state theory, dynamics trajectories, and a review of previous dynamics studies of organometallic reactions. Chapter 2 reports dynamics trajectories of an organometallic β–hydride transfer reaction with Rh, Ir, and Co metal centers. This chapter was previously published as Dalton Trans. 2020, 49, 7747-7757. Chapters 3 reports the potential energy surface and structures for benzene reductive elimination for dimethyl silyl-bridged W and Mo metallocene complexes. Chapter 4 reports gas-phase and explicit solvent dynamics trajectories for this benzene reductive elimination reaction.
Degree
PhD
College and Department
Chemistry and Biochemistry; Computational, Mathematical, and Physical Sciences
Rights
https://lib.byu.edu/about/copyright/
BYU ScholarsArchive Citation
Wheeler, Joshua I., "Computational Modeling of Energy Landscapes and Trajectory Studies of Fundamental Organometallic Reactions" (2023). Theses and Dissertations. 10541.
https://scholarsarchive.byu.edu/etd/10541
Date Submitted
2023-08-10
Document Type
Dissertation
Handle
http://hdl.lib.byu.edu/1877/etd13379
Keywords
Density functional theory, transition state theory, energy landscapes, organometallic, quasiclassical, molecular dynamics, direct dynamics, explicit solvent
Language
english