Document Detail


2-hydroxypyridine <--> 2-pyridone tautomerization: catalytic influence of formic acid.
MedLine Citation:
PMID:  16854025     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
A 1:1 hydrogen-bonded complex between 2-pyridone and formic acid has been characterized using laser-induced-fluorescence excitation and dispersed fluorescence spectroscopy in a supersonic jet expansion. Under the same expansion condition, the fluorescence signal of the tautomeric form of the complex (2-hydroxypyridine...formic acid) is absent, although both the bare tautomeric molecules exhibit well-resolved laser-induced-fluorescence spectra. Quantum chemistry calculation at the DFT/B3LYP/6-311++G** level predicts that in the ground electronic state the activation barrier for tautomerization from hydroxy to keto form in bare molecules is very large (approximately 34 kcal/mol). However, the process turns out to be nearly barrierless when assisted by formic acid, and double proton transfer occurs via a concerted mechanism.
Authors:
Montu K Hazra; Tapas Chakraborty
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  110     ISSN:  1089-5639     ISO Abbreviation:  J Phys Chem A     Publication Date:  2006 Jul 
Date Detail:
Created Date:  2006-07-20     Completed Date:  2007-08-14     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  9130-6     Citation Subset:  IM    
Affiliation:
Department of Chemistry, Indian Institute of Technology, Kanpur, UP 208016, India.
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MeSH Terms
Descriptor/Qualifier:
Catalysis
Electrons
Formic Acids / chemistry*
Isomerism
Models, Molecular
Molecular Conformation
Pyridones / chemistry*
Spectrometry, Fluorescence
Chemical
Reg. No./Substance:
0/Formic Acids; 0/Pyridones; 142-08-5/2-hydroxypyridine; 64-18-6/formic acid

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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