Structure and bonding of Ag(I)–DNA base complexes and Ag(I)–adenine–cytosine mispairs: An ab Initio study

High level ab initio calculations have been carried out to characterize the structure, bonding and energetics of Ag(I)–DNA base complexes, including adenine or cytosine, as well as Ag(I)–adenine–cytosine mispairs. The interactions of the Ag cation in all binding sites of all adenine and cytosine tautomers have been considered. The calculations show that in gas phase the canonical form of cytosine is stabilized upon metalation, whereas the lowest energy structure of Ag–adenine correspond to a rare tautomer. Interestingly, the theoretical inspection of metalated adenine–cytosine mispair reveals that the most stable structures are formed from the canonical cytosine and adenine tautomers. The lowest energy structure is planar with adenine and cytosine hydrogen‐bonded. Within few kcal/mol nonplanar, conformationally very flexible structures are found, in which the Ag(I) crosslinks an endocyclic nitrogen of adenine and the oxygen of cytosine. Metalated reverse‐Wobble type of structures, on the contrary, are predicted much higher in energy.