Proton or Metal? The H/D Exchange of Arenes in Acidic Solvents
Abstract
The H/D exchange of arenes in acidic media by transition-metal and main-group-metal complexes and common inorganic salts was studied. The influence of Lewis acidity, anions, charge, and ligands was evaluated. The results indicate that the determination of H/D exchange activity in acidic media is not related to the formation of metal–carbon bonds (i.e., C–H activation). The combined experimental data (regioselectivity, activation energy, kinetics, isotope effects, solvent effects) and DFT calculations point toward a proton catalysis mechanism. Thus, highly Lewis acidic metal compounds, such as aluminum(III) triflate, were extraordinarily active for the H/D exchange reactions. Indeed, the degree of H/D exchange reactivity allows for a comparative measurement of Lewis acidities.
Additional Information
© 2014 American Chemical Society. Received: October 20, 2014; Revised: December 14, 2014; Published: December 30, 2014. This work was supported as part of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0001298. Generous donations of HOTFA by Solvay Fluor are gratefully acknowledged.Attached Files
Supplemental Material - cs501620f_si_001.pdf
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Additional details
- Eprint ID
- 55760
- Resolver ID
- CaltechAUTHORS:20150313-150419261
- Department of Energy (DOE)
- DE-SC0001298
- Created
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2015-03-13Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field