Open AccessOpen-Resonance-Assisted Hydrogen Bonds and Competing Quasiaromaticity
Author(s) -
Yen Nguyen,
Bryan J. Lampkin,
Amrit Venkatesh,
Arkady Ellern,
Aaron J. Rossini,
Brett VanVeller
Publication year - 2018
Publication title -
the journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.2
H-Index - 228
eISSN - 1520-6904
pISSN - 0022-3263
DOI - 10.1021/acs.joc.8b01331
Subject(s) - tautomer , chemistry , delocalized electron , isomerization , hydrogen bond , resonance (particle physics) , conjugated system , electron delocalization , hydrogen , computational chemistry , aromaticity , photochemistry , chemical physics , stereochemistry , molecule , catalysis , organic chemistry , atomic physics , polymer , physics
The delocalization of electron density upon tautomerization of a proton across a conjugated bridge can alter the strength of hydrogen bonds. This effect has been dubbed resonance-assisted hydrogen bonding (RAHB) and plays a major role in the energetics of the tautomeric equilibrium. The goal of this work was to investigate the role that π-delocalization plays in the stability of RAHBs by engaging other isomerization processes. Similarly, acid-base chemistry has received little experimental attention in studies of RAHB, and we address the role that acid-base effects play in the tautomeric equilibrium. We find that π-delocalization and the disruption of adjacent aromatic rings is the dominant effect in determining the stability of a RAHB.
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