da Costa Gouveia Tiago Leyser, Campos Renan Borsoi, Ribeiro Ronny Rocha, Nunes Fábio Souza
Departamento de Química, Universidade Federal do Paraná, Cx. Postal 19081, 81531-980, Curitiba, PR, Brazil.
Departamento Acadêmico de Química e Biologia, Universidade Tecnológica Federal do Paraná, 81280-340, Curitiba, PR, Brazil.
J Comput Chem. 2019 Jun 15;40(16):1593-1598. doi: 10.1002/jcc.25810. Epub 2019 Mar 3.
Penta(ammine)ruthenium benzotriazole complexes [Ru (NH ) bta] and [Ru (NH ) btaH] (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κN1 and κN2. This system was investigated by density functional theory natural bond orbitals analysis and Su-Li energy decomposition analysis. Steric, electrostatic, exchange, repulsion, polarization, and dispersion energy components of the total metal-ligand interaction were quantitatively evaluated, and revealed that the overall metal-triazole ligand is comprised of donor-acceptor interactions like σ-donation and π-back-donation, which favors a specific isomer depending on the oxidation state of the ruthenium and the charge of the ligand. Further, activation energies (ΔG ) for linkage isomerization reactions were calculated. Results were correlated with experimental chemical-electrochemical data and two plausible mechanisms are discussed. © 2019 Wiley Periodicals, Inc.
