Zvaná přednáška – Jana Roithová

Understanding reaction mechanisms is the key to developing new chemical reactions. Electrospray ionization mass spectrometry has a unique dynamic range that allows the study of reaction mixture compositions, including low-abundant reactive intermediates. In the lecture, I will show several approaches to studying reaction kinetics via mass spectrometry coupling with flow-chemistry or batch-chemistry setups.^[1-3]

Monitoring the kinetics associated with the reactive intermediates opens a way to understand the effects of catalysts and other reaction mixture components on forming products and by-products. One of the rising fields in catalysis is electrocatalysis. However, processes at the electrodes are extremely difficult to study. However, electron transfer processes usually generate charged species; therefore, mass spectrometry can be an ideal tool to study these processes, provided we have an efficient way of transferring the generated species to a mass spectrometer. I will present our solution, allowing us to study the electrochemically generated intermediates and evaluate their kinetics at an electrode.^[5,6] We also couple the setup with cryogenic ion spectroscopy and study the structure of the reactive intermediates by vibrational and electronic spectroscopy.^[4]

1. J. Mehara, J. Roithova, Identifying reactive intermediates by mass spectrometry, Chem. Sci. 11 (2020) 11960.
2. G. L. Tripodi et al., Tracking Reaction Pathways by a Modular Flow Reactor Coupled to Electrospray Ionization Mass Spectrometry, Chem. Methods 1 (2021) 430.
3. J. Mehara et al., Competing Mechanisms in Palladium-Catalyzed Alkoxycarbonylation of Styrene, ACS Catal. 14 (2024) 5710.
4. J. Roithová et al., Helium Tagging Infrared Photodissociation Spectroscopy of Reactive Ions, Acc. Chem. Res. 49 (2016) 223.
5. A. Bairagi et al., Electrocatalytic CO2 Reduction: Monitoring of Catalytically Active, Downgraded, and Upgraded Cobalt Complexes, J. Am. Chem. Soc. 146 (2024), 5480.
6. A. Koovakattil Surendran et al., Intricacies of Mass Transport during Electrocatalysis: A Journey through Iron Porphyrin-Catalyzed Oxygen Reduction, J. Am. Chem. Soc. 146 (2024), 15619.