Resonance-Assisted Hydrogen Bonds: A Critical Examination. Structure and Stability of
the Enols of β-Diketones and β-Enaminones
Pablo Sanz
Otilia Mó
Manuel Yáñez
José Elguero
10.1021/jp067514q.s001
https://acs.figshare.com/articles/journal_contribution/Resonance_Assisted_Hydrogen_Bonds_A_Critical_Examination_Structure_and_Stability_of_the_Enols_of_Diketones_and_Enaminones/3008329
The characteristics of the intramolecular hydrogen bond (IMHB) for a series of 40 different enols of β-diketones
and their nitrogen counterparts have been systematically analyzed at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. In some cases, two tautomers may exist which are interconnected by a hydrogen
shift through the IMHB. In tautomer <b>a</b> the HB donor group (YH) is attached to the six-membered ring, while
in tautomer <b>b</b> the HB acceptor (X) is the one that is attached to the six-membered ring. We found that
changing an O to a N favors the <b>a</b> tautomer when the atom is endo and the contrary when it is exo, while the
presence of a double bond favors the <b>a</b> tautomers. As expected, the OH group behaves as a better HB donor
than the NH<sub>2</sub> group and the CNH group as a better HB acceptor than the CO group, although the first
effect clearly dominates. Accordingly, the expected IMHB strength follows the [donor, acceptor] trend: [OH,
CNH] > [OH, CO] > [NH<sub>2</sub>, CNH] > [NH<sub>2</sub>, CO]. For all those compounds in which the functionality
exhibiting the IMHB is unsaturated (<b>I</b>-type), the IMHB is much stronger than in their saturated counterparts
(<b>II</b>-type). However, when the systems of the <b>II</b>-type subset, which are saturated, are constrained to have the
HB donor and the HB acceptor lying in the same plane and at the same distance as in the corresponding
unsaturated analogue, the IMHB is of similar or even larger strength. Hence, we conclude that, at least for
this series of unsaturated compounds, the resonance-assisted hydrogen bond effect is not the primary reason
behind the strength of their IMHBs, which is simply a consequence of the structure of the σ-skeleton of the
system that keeps the HB donor and the HB acceptor coplanar and closer to each other.
2007-05-10 00:00:00
IMHB
HB donor group
HB acceptor
OH
HB donor
HB acceptor coplanar
NH 2 group
intramolecular hydrogen bond
strength
B 3LYP level
tautomer
YH