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Hyperconjugative effects in π‐hydrogen bonding: Theory and experiment
Author(s) -
Galabov Boris,
Nikolova Valia,
Cheshmedzhieva Diana,
Hadjieva Boriana,
Schaefer Henry F.
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25088
Subject(s) - hexamethylbenzene , chemistry , density functional theory , hydrogen bond , computational chemistry , benzene , hydrogen , molecule , organic chemistry
Density functional theory computations with the B3LYP/6‐311++G(2df,2p) method and IR spectroscopy are employed in investigating the properties of twenty π‐hydrogen bonded complexes between substituted phenols and hexamethylbenzene. All complexes possess T‐shaped structures. The methyl hyperconjugative effects on interactions energies and OH stretching frequencies are estimated via comparisons with previously reported theoretical and experimental results for analogous phenol complexes with benzene. The theoretical computations provide excellent quantitative predictions of the OH stretching frequency shifts (Δ ν OH ) resulting from the hydrogen bonding. The Δ ν OH shifts in the hexamethylbenzene complexes are approximately twice as large as the corresponding shifts for the benzene complexes. Hirshfeld charges, electrostatic potential at nuclei values, and molecular electrostatic potential maps are employed in gaining insights into the mechanisms of methyl hyperconjugative effects on complex formation. © 2017 Wiley Periodicals, Inc.