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Spectroscopic evidence for medium controlled hydrogen bond inhibition of resonance delocalization of charge in complexes of tetrabutylammonium fluoride with phenols
Affiliation:1. Department of Architecture, University of Palermo, Italy;2. “Schiavello-Grillone” Photocatalysis Group, Dipartimento di Energia, Ingegneria dell''informazione, e modelli Matematici (DEIM), University of Palermo, Viale delle Scienze, 90128, Palermo, Italy;1. Univ Lyon, Université Claude Bernard Lyon 1, ISPB-Faculté de Pharmacie, EA 4446, B2MC, F-69373, Lyon Cedex 08, France;2. Univ Lyon, Université Claude Bernard Lyon 1, VetAgro Sup, UMR CNRS 5557, Ecologie Microbienne, F-69622 Villeurbanne, France;3. Laboratoire de Bactériologie, Centre de Biologie et Pathologie Est, Hospices Civils de Lyon (HCL), F-69000 Bron, France;1. Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China;2. Chemistry Department, College of Saint Benedict and Saint John’s University, MN 56374, USA;1. Departamento de Química Orgánica, Universidad de Valencia, 46100 Burjassot, Spain;2. Laboratorio de Moléculas Orgánicas, Centro de Investigación Príncipe Felipe, 46012 Valencia, Spain;1. Guangxi Key Laboratory of Forest Ecology and Conservation, College of Forestry, Guangxi University, Nanning, Guangxi, China;2. Center for Integrative Conservation, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Science, Menglun, Mengla, Yunnan, China
Abstract:Infrared spectra of tetrabutylammonium fluoride complexes of both 4-cyanophenol and methyl-4-hydroxybenzoate but not 3-cyanophenol reveal the presence of two distinct types of hydrogen bond corresponding to charge localized and partially charge delocalized forms. The latter only occur in polar aprotic protophilic solvents at low temperatures. The activation energies for the interconversion of the two forms reflect the relative abilities of the two groups to delocalize charge through resonance. The chemical shifts of the aromatic protons of the complexes are also medium dependent although the precise nature of this medium dependence is less easily understood.
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