Ab initio molecular dynamics study of the keto-enol tautomerism of acetone in solution (Articolo in rivista)

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  • Ab initio molecular dynamics study of the keto-enol tautomerism of acetone in solution (Articolo in rivista) (literal)
Anno
  • 2006-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1002/cphc.200600007 (literal)
Alternative label
  • Cucinotta C.S. a,b; Ruini A. a,b; Catellani A. a,c; Stirling A. d (2006)
    Ab initio molecular dynamics study of the keto-enol tautomerism of acetone in solution
    in ChemPhysChem (Print); WILEY-V C H VERLAG GMBH,, D-69451 WEINHEIM, (Germania)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Cucinotta C.S. a,b; Ruini A. a,b; Catellani A. a,c; Stirling A. d (literal)
Pagina inizio
  • 1229 (literal)
Pagina fine
  • 1234 (literal)
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  • 7 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 6 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • a CNR, INFM, Natl Ctr NanoStruct & Biosyst Surfaces S3, I-00185 Rome, Italy; b Univ Modena, Dipartimento Fis, I-41100 Modena, Italy; c CNR-IMEM, I-43010 Parma, Italy; d Chem Res Ctr, Dept Theoret Chem, H-1525 Budapest, Hungary (literal)
Titolo
  • Ab initio molecular dynamics study of the keto-enol tautomerism of acetone in solution (literal)
Abstract
  • We have studied the keto-enol interconversion of acetone to understand the mechanism of tautomerism relevant to numerous organic and biochemical processes. Applying the ab initio metadynamics method, we simulated the keto-enol isomerism both in the gas phase and in the presence of water. For the gas-phase intramolecular mechanism we show that no other hydrogen-tronsfer reactions can compete with the simple keto-enol tautomerism. We obtain an intermolecular mechanism and remarkable participation of water when acetone is solvated by neutral water. The simulations reveal that C deprotonation is the kinetic bottleneck of the keto-enol transformation, in agreement with experimental observations. The most interesting finding is the formation of short H-bonded chains of water molecules that provide the route for proton transfer from the carbon to the oxygen atom of acetone. The mechanistic picture that emerged from the present study involves proton migration and emphasizes the importance of active solvent participation in tautomeric interconversion. (literal)
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