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Capturing Transient and Intermediate States of Coordination Chemistry Under High PressureArchambault, Cynthia Megan 12 1900 (has links)
This dissertation aims to establish experimental methods to characterize transient states of chemical reactions by stabilizing transient states using mechanical stress. We argue that gigapascal (GPa)-level pressure produces deformed molecular structures that approximate the transient states along the reaction coordinate on the ground-state surface, thereby fundamentally understanding their mechanism through high-pressure mechanochemistry. By varying the pressure, the entire reaction path can be quasi-statically traversed and characterized with steady-state measurements. This strategy is experimentally implemented using a diamond anvil cell and in situ spectroscopy and highlighted in experimentation with three model systems. Two models investigate dicopper peroxo-centered isomerizations which are vastly found in nature within coupled binuclear copper centers. The cis-, trans-, and side-on peroxo and bis-(µ -oxo) isomers each play a unique and crucial role in the type (III) copper catalytic cycles. Through thes
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