Gas‐Phase Reactivity of Uracil, 2‐Thiouracil, 4‐Thiouracil, and 2,4‐Dithiouracil towards the Cu⁺ Cation: A DFT Study

Abstract

80 Cu+–(thio)uracil structures were investigated by DFT calculations, which, with the exception of 2-thiouracil, showed that attachment of the Cu+ cation occurs initially at the heteroatom at position 4. For uracil–Cu+, 2-thiouracil–Cu+, and 2,4-dithiouracil–Cu+ in the global minimum the Cu+ cation bridges the heteroatom at position 2 and an adjacent amino group of the corresponding enolic tautomer. Isomerization processes leading from the most stable adduct to the global minimum (shown for 2-thiouracil in the picture, with energies in kJ mol−1) and to other stable conformers were also investigated. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2267/2003/z704_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.