Ćoćić Dušan, Petrović Biljana, Puchta Ralph, Chrzanowska Marta, Katafias Anna, van Eldik Rudi
Department of Chemistry, Faculty of Science, University of Kragujevac, Kragujevac.
Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Erlangen, Germany.
J Comput Chem. 2022 Jun 30;43(17):1161-1175. doi: 10.1002/jcc.26878. Epub 2022 Apr 29.
In this paper, we investigated water exchange reactions and substitution of aqua Ru complexes of general formula [Ru(terpy)(N^N)(H O)] (where N^N = ethylenediamine (en), 1,2-(aminomethyl)pyridine (ampy) and 2,2'-bipyridine (bipy)) by ammonia and thioformaldehyde. These reactions were studied in detail by applying conceptual density functional theory. This approach enabled us to gain further insight into the underlying reaction mechanism at the microscopic level (involving only direct participants of the reaction, without the influence of the solvent) and to put the concept of reaction mechanism on a quantitative basis. The course of the chemical reaction along the reaction coordinate ξ, is rationalized in terms of reaction energy, force, dipole moment, and reaction electronic flux (REF). The results yield and characterize the significant influence of an intermolecular hydrogen bond formed between the entering and the spectator ligand to the overall energy barrier of the reactions.
