The role of intramolecular hydrogen bonding on nucleobase acidification following metal coordination: possible implications of an "indirect" role of metals in acid-base catalysis of nucleic acids.
The acidifying effect of Pt(II) on nucleobase -NH and -NH2 groups depends both on the site of metal coordination and on the efficiency of stabilization of the deprotonated nucleobase via intracomplex hydrogen bonding. Weakly acidic nucleobase protons with pK (a) values between 9 and 17 can be acidified by a single Pt(II) to have pK (a) values which are well within the physiological pH range. This could open the possibility of an acid-base catalysis occurring at pH 7, with the metal-nucleobase entity functioning either as an acid or a base. Examples of Pt(II) complexes studied here include, among others, mixed nucleobase systems of 1-methylcytosine and 1,9-dimethyladenine as well as a complex of the rare iminooxo tautomer of 1-methylcytosine having the metal bonded at N4.
Roitzsch
Michael
M
Fachbereich Chemie, Universität Dortmund, Otto-Hahn-Strasse 6, 44221, Dortmund, Germany.
Añorbe
Marta Garijo
MG
Miguel
Pablo J Sanz
PJ
Müller
Barbara
B
Lippert
Bernhard
B
D002384:Catalysis; D018360:Crystallography, X-Ray; D003596:Cytosine / Q000031:analogs & derivatives / Q000737:chemistry; D006860:Hydrogen Bonding; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D009696:Nucleic Acids / Q000737:chemistry*; D009711:Nucleotides / Q000737:chemistry*
D008670:Metals; D009696:Nucleic Acids; D009711:Nucleotides; C031532:1-methylcytosine; D003596:Cytosine