Real-time mass spectrometric analysis of catalytic reaction mechanisms




Yunker, Lars Peter Erasmus

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Mass spectrometry was used to study two disparate transformations: in an applied project, the supposed degradation of perfluorooctanesulfonate (PFOS); and in a fundamental study, the Suzuki-Miyaura (SM) reaction was investigated in detail. The first investigation revealed that published methods to degrade PFOS were ineffectual, with apparent decreases being associated with adsorption onto available surfaces. In the Suzuki-Miyaura reaction, a dynamic series of equilibria were observed, and there is no direct evidence of a single pathway. Instead, there appear to be two mechanisms which are active in different conditions (one fluoride, one aqueous). Studies were initiated into the related SM polycondensation reaction and the hydrolysis of aryltrifluoroborates, the former indicating a step-growth mechanism, and the latter indicating a dynamic series of equilibria which are very sensitive to experimental conditions. Processing and interpretation of mass spectrometric data was a significant part of all of these projects, so a python framework was developed to assist in these tasks and its features are also documented herein.



Mass spectrometry, Suzuki-Miyaura, online reaction monitoring, electrospray ionization, ESI-MS, perfluorooctane sulfonate, PFOS, transmetallation mechanism, trifluoroborate hydrolysis, suzuki polycondensation, python, MSPT, pressurized sample infusion