Following molecular mobility during chemical reactions: no evidence for active propulsion
| Autor: | Peer Fischer, Jan-Philipp Günther, Lucy L. Fillbrook, Jonathon E. Beves, William S. Price, Daniel J. O'Leary, Hal Van Ryswyk, Günter Majer |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Reaction mechanism
010405 organic chemistry Chemistry Relaxation (NMR) General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Chemical reaction Catalysis Cycloaddition 0104 chemical sciences Chemical kinetics Colloid and Surface Chemistry Catalytic cycle 13. Climate action Chemical physics Molecule Diffusion (business) |
| Zdroj: | Journal of the American Chemical Society |
| Popis: | The measured changes in self-diffusion of small molecules during reactions have been attributed “boosted mobility”. We demonstrate the critical role of changing concentrations of paramagnetic ions on nuclear magnetic resonance (NMR) signal intensities, which lead to erroneous measurements of diffusion coefficients. We present simple methods to overcome this problem. The use of shuffled gradient amplitudes allows accurate diffusion NMR measurements, even with time-dependent relaxation rates caused by changing concentrations of paramagnetic ions. The addition of a paramagnetic relaxation agent allows accurate determination of both diffusion coefficients and reaction kinetics during a single experiment. We analyze a copper-catalyzed azide-alkyne cycloaddition ‘click’ reaction, for which boosted mobility has been claimed. With our methods, we accurately measure the diffusive behavior of solvent, starting materials and product, and find no global increase in diffusion coefficients during the reaction. We overcome NMR signal overlap using an alternative reducing agent to improve the accuracy of the diffusion measurements. The alkyne reactant diffuses slower as the reaction proceeds, due to binding to the copper catalyst during the catalytic cycle. The formation of this intermediate was confirmed by complementary NMR techniques and density functional theory calculations. Our work calls into question recent claims that molecules actively propel or swim during reactions, and establishes that time-resolved diffusion NMR measurements can provide valuable insight into reaction mechanisms. |
| Databáze: | OpenAIRE |
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