The hydrogen bond strength of the phenol–phenolate anionic complex: a computational and photoelectron spectroscopic study

文献情報

出版日 2015-09-02

DOI 10.1039/C5CP04754D

インパクトファクター 3.676

著者

Allyson M. Buytendyk, Jacob D. Graham, Kim D. Collins, Kit H. Bowen, Chia-Hua Wu, Judy I. Wu

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要旨

The phenol–phenolate anionic complex was studied in vacuo by negative ion photoelectron spectroscopy using 193 nm photons and by density functional theory (DFT) computations at the ωB97XD/6-311+G(2d,p) level. We characterize the phenol–phenolate anionic complex as a proton-coupled phenolate pair, i.e., as a low-barrier hydrogen bond system. Since the phenol–phenolate anionic complex was studied in the gas phase, its measured hydrogen bond strength is its maximal ionic hydrogen bond strength. The D(PhO−⋯HOPh) interaction energy (26–30 kcal mol−1), i.e., the hydrogen bond strength in the PhO−⋯HOPh complex, is quite substantial. Block-localized wavefunction (BLW) computations reveal that hydrogen bonded phenol rings exhibit increased ring π-electron delocalization energies compared to the free phenol monomer. This additional stabilization may explain the stronger than expected proton donating ability of phenol.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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