Intramolecular Hydrogen Bonding Effect on the Electron-Transfer Thermodynamics of a Series of o‑Nitrobenzyl Alcohol Derivatives

From thermoelectrochemical experiments and electronic structure calculations of a series of nitrobenzyl alcohol derivatives, the effect of intramolecular hydrogen bonding (IHB) on the electron transfer thermodynamics is discussed on a molecular basis. A linear correlation between formal reduction po...

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Bibliographic Details
Published in:Journal of organic chemistry 2023-08, Vol.88 (16), p.11434-11443
Main Authors: Enriquez-Izazaga, Y., Rodriguez-Nuñez, J. A., Frontana, C., Armendariz-Vidales, G.
Format: Article
Language:English
Subjects:
alcohols
electron transfer
enthalpy
entropy
hydrogen
organic chemistry
temperature
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Summary:From thermoelectrochemical experiments and electronic structure calculations of a series of nitrobenzyl alcohol derivatives, the effect of intramolecular hydrogen bonding (IHB) on the electron transfer thermodynamics is discussed on a molecular basis. A linear correlation between formal reduction potential (E 1/2) values and temperature was obtained for the temperature range from 300 to 350 K. Estimated electron transfer entropy values (ΔS)determined from this dependenceand the enthalpy (ΔΔH) changes relative to o-nitrobenzyl alcohol confirmed that the effect of the formation of IHB proved to be decisive in the charge-transfer thermodynamics. The possibility of intermolecular hydrogen bonding is further discussed upon comparing thermodynamic data among three different solvents.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.3c00180