Journal
CHEMPHYSCHEM
Volume 16, Issue 11, Pages 2375-2382Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201500262
Keywords
copper; nucleobases; proton transfer; reaction mechanisms; tautomerism
Funding
- Ministerio de Economia y Competitividad [CTQ2012-35513-C02-01, CTQ2013-43698-P]
- STSM COST Action [CM1204]
- Comunidad Autonoma de Madrid [FOTOCARBON-CM S2013/MIT-2841]
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The reaction-force formalism is applied to carry out a detailed analysis of the mechanisms behind the enolization processes undergone by the complexes formed on interaction of uracil dimers with Cu2+ ions after spontaneous deprotonation of the resulting complexes. These enolization processes apparently involve a single proton transfer (PT) from an NH group to a carbonyl group of the same uracil moiety, which should involve a rather high activation barrier that prevents the process occurring. However, the reaction-force, chemical-potential, and electronic-flux profiles unambiguously indicate that the actual mechanism involves three low-barrier elementary steps, and this explains why enolization of the [Cu(uracil-H)(uracil)](+) complexes is a highly facile, assisted PT process. All of the observed PT processes show a typical profile for both the chemical potential and the electronic flux associated with the bond-breaking and the bond-formation processes.
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