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.