Predicting the stability constants of metal-ion complexes from first principles

0423986 - ÚOCHB 2014 RIV US eng J - Článek v odborném periodiku
Gutten, Ondrej - Rulíšek, Lubomír
Predicting the stability constants of metal-ion complexes from first principles.
Inorganic Chemistry. Roč. 52, č. 18 (2013), s. 10347-10355. ISSN 0020-1669. E-ISSN 1520-510X
Institucionální podpora: RVO:61388963
Klíčová slova: stability constants * solvation energy * metal-ion complexation * theoretical calculations * DFT methods
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 4.794, rok: 2013

The most important experimental quantity describing the thermodynamics of metal-ion binding with various (in)organic ligands, or biomolecules, is the stability constant of the complex (beta). It can be calculated as the free-energy change associated with the metal-ion complexation, i.e., its uptake from the solution under standard conditions. We use density functional theory and Moller-Plesset second-order perturbation theory calculations together with the conductor-like screening model for realistic solvation to calculate the stability constants of selected complexes--[M(NH3)4](2+), [M(NH3)4(H2O)2](2+), [M(Imi)(H2O)5](2+), [M(H2O)3(His)](+), [M(H2O)4(Cys)], [M(H2O)3(Cys)], [M(CH3COO)(H2O)3](+), [M(CH3COO)(H2O)5](+), [M(SCH2COO)2](2-)--with eight divalent metal ions (Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Hg(2+)). We show that it is possible to achieve a relative accuracy of 2-4 kcal?mol(-1). Finally, a critical discussion is presented that aims at potential caveats that one may encounter in theoretical predictions of the stability constants and highlights the perspective that theoretical calculations may become both competitive and complementary tools to experimental measurements.
Trvalý link: http://hdl.handle.net/11104/0230152