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The hydrogen bond strength of the phenol-phenolate anionic complex: a computational and photoelectron spectroscopic
Allyson M Buytendyk1, Jacob D Graham, Kim D Collins
1Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA. kbowen@jhu.edu.
Abstract:
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.
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