Coexistence of major and minor tautomers of 1-methylcytosine (1-MeC) in a single metal complex, trans-Pt(1-MeC-N3)(1-MeC-N4)X-2 (X = Cl, I): metal migration N3 -> N4 at acidic pH

摘要

Two complexes of composition trans-Pt(1-MeC-N3)(1-MeC-N4)I-2 . 2H(2)O (4) and trans-Pt(1-MeC-N3)(1-MeC-N4)Cl-2 (5) are described and characterized by X-ray analysis, which simultaneously contain the preferred aminooxo tautomer I and the rare iminooxo tautomer II of 1-methyleytosine (1-MeC) bonded to the heavy metal, via N3 and N4, respectively. Formation of 4 originates from [Pt(1-MeC-N3)(3)I]I (2), which likewise has been characterized by X-ray crystal structure analysis. A feasible way of formation of 4, which involves a metal migration process from N3 to N4 occurring at moderately acidic pH, is proposed. It appears to be yet another mechanism of metal migration, different from previously established cases which are redox-assisted and hydroxide-promoted, respectively. (C) 2004 Elsevier B.V. All rights reserved.