Metal‐stabilized rare tautomers: N4 metalated cytosine (M = Li+, Na+, K+, Rb+ and Cs+), theoretical views
Citations Over Time
Abstract
Abstract Ab initio calculations indicate that metalation of the exocyclic amino group of cytosine by the elements of Group IA (Li, Na, K, Rb and Cs) induces protonation of a nucleobase ring nitrogen atom, and hence causes a proton shift from an exocyclic to an endocyclic nitrogen atom. Thus, this metal‐assisted process leads to the generation of rare nucleobase tautomers. The calculations suggest that this kind of metalation increases the protonation energies of the aromatic ring of the nucleobase. The present study reports the quantum chemistry analysis of the metal‐assisted tautomerization. The calculations clearly demonstrate that metalation of the exocyclic amino group of the nucleobase significantly increases the protonation energy of the aromatic rings of the nucleobase. Also, absolute anisotropy shift, molecular orbital and natural bond orbital calculations are compatible with these results. Copyright © 2003 John Wiley & Sons, Ltd.
Related Papers
- → Azo-hydrazone tautomerism of hydroxyazo compounds—a review(1982)140 cited
- → Promotion of rare nucleobase tautomers by metal binding(2009)77 cited
- → Atomic-Scale Investigation on the Facilitation and Inhibition of Guanine Tautomerization at Au(111) Surface(2014)40 cited
- → Studies on the Tautomerism of 2-Anilinopyridine and Related Heterocycles. II. 2-Anilino-5-nitropyridine and 2-Anilinopyrimidine(1980)9 cited
- → ChemInform Abstract: Metal‐Stabilized Rare Tautomers of Nucleobases. Part 2. 2‐Oxo‐4‐hydroxo Form of Uracil: Crystal Structures and Solution Behavior of Two Platinum(II) Complexes Containing Iminol Tautomers of 1‐Methyluracil.(1989)