A Computational approach toward organometallic ruthenium(II) compounds with tunable hydrolytic properties

Abstract

The present study aimed to assess the structures and electronic properties, charge distribution, and thermodynamic feasibility of isolation of six organometallic compounds with general formula [Ru(η6-arene-R)(en)Cl]+, where R is one of the electron-donor/-acceptor groups: N(CH3)2, SCH3, CH3, H, OCF3, and CF3, comparing with the already synthesized compound [Ru(η6-anethole)(en)Cl]+, where R = OCH3. Different DFT functionals were employed to analyze minimum global structures, HOMO/LUMO and TDDFT gaps, NBO charges and energies of formation. MOs analysis showed a systematic drop of the HOMO and LUMO energy levels upon replacing R = OCH3 by SCH3, CH3, H, OCF3, and CF3. The NBO analysis revealed that the R group variation would more significantly affect the charges on the Ru- and Cl-atoms, thus influencing the hydrolysis of this kind of compounds. Finally, binding energies/free energies of formation showed that the compounds with R = H, CH3, and SCH3 should be feasible to be prepared.