title: On the stability of [(uracil)2-Cu]2+ complexes in the gas phase. Different pathways for the formation of [(uracil-H)(uracil)-Cu]+ monocations.
abstract: The association of uracil dimers and copper(II) has been studied through the use of B3LYP/6-311+G(3df,2p)//6-31+G(d,p) calculations. Although uracil-Cu(2+) complexes have never been experimentally detected, our results show that [(uracil)2-Cu](2+) is thermodynamically stable with regard to both the proton loss and the fragmentation into (uracil)2(+)˙ + Cu(+), although it is metastable with respect to the coulomb explosion yielding [uracil-Cu](+) + uracil(+)˙. Importantly, a proton transfer from [(uracil)2-Cu](2+) to a third neutral uracil molecule is very exothermic. This is consistent with the fact that when electrospray mass spectrometry techniques are used [(uracil-H)(uracil)-Cu](+) and uracil-H(+) monocations are detected, but not the [(uracil)2-Cu](2+) doubly charged species. In the most stable conformers of [(uracil)2-Cu](2+) the two uracil monomers are held together through the metal cation which forms a linear bridge between two carbonyl groups each belonging to a different monomer. This is at variance with what has been found for complexes involving alkaline-earth dications, such as (uracil)2Ca(2+), in which the metal dication association preserves the network of hydrogen bonds which stabilize the free (uracil)2 dimers. The formation of [(uracil-H)(uracil)-Cu](+) complexes is accompanied by the enolization of the uracil units. All possible mechanisms to reach the experimentally detected [(uracil-H)(uracil)-Cu](+) singly charged ions, either by direct association of Cu(2+) to uracil dimers and posterior deprotonation of the formed complex or through the interaction of Cu(2+) with uracil followed by its deprotonation and subsequent association with a second uracil molecule, have been investigated.
authors: Departamento de Química, Facultad de Ciencias, Módulo 13, Campus de Excelencia UAM-CSIC, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain.
authors: Oriana
authors: O
authors: Brea
authors: Manuel
authors: M
authors: Yáñez
authors: Otilia
authors: O
authors: Mó
authors: Al Mokhtar
authors: AM
authors: Lamsabhi
mesh_terms: D003300:Copper / Q000737:chemistry*; D004355:Drug Stability; D005740:Gases / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D013696:Temperature; D014498:Uracil / Q000737:chemistry*
chemical_list: D005740:Gases; D009942:Organometallic Compounds; D014498:Uracil; D003300:Copper