Shedding light on the electronic structure of [Ru((6)-C16H16)(NH3)(3)](2+) complex: a computational insight

Author(s)

Orenha, Renato P. ^[1] ; Caramori, Giovanni F. ^[2] ; Misturini, Alechania ^[2] ; Galembeck, Sergio E. ^[1]

Affiliation

^[1] Univ Sao Paulo, FFCLRP, Dept Quim, BR-14040901 Ribeirao Preto, SP - Brazil

^[2] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

• Document type: Journal article
• Source: Journal of Molecular Modeling; v. 25, n. 1 JAN 2019.
• Web of Science Citations: 0

Abstract

Ruthenophanes have been recognized as potential candidates to the design of electrically conducting polymers, particularly due to their electrochemical, structural, and spectroscopic properties. The comprehension and rationalization of the metal-ligand interaction is fundamental to pave the way for future applications as the design of new conducting materials. For that reason, this investigation sheds light on the electronic details behind the cation- interactions present in ruthenophanes by using {[}Ru((6)-C16H16)(NH3)(3)](2+) as a model. Zeroth-order symmetry-adapted perturbation theory (SAPT0) shows the interaction Ru(II)-{[}2.2]paracyclophane with a predominant covalent character. However, the hapticity analysis of {[}2.2]paracyclophane shows only two predominantly covalent Ru-C bonds, as highlighted by the total energy density, H(r), in the bond critical point (BCP) obtained from quantum theory of atoms in molecules (QTAIM) method, and by second-order stabilization energy, E-(2), related to the processes: C-C d(sigma) or d Ru, achieved in the natural bond orbital (NBO) method. The other two Ru-C chemical bonds show a largely electrostatic character, as can be visualized from the delocalization index, DI, between the electron basins in the electron localization function (ELF) method. Remarkably, the interacting quantum atoms (IQA) method showed practically the same value of the total interaction energy, EintAB, between Ru and these C atoms and, then, corroborates the hapticity four of the ligand: {[}2.2]paracyclophane. Source function distribution presents a correlation with the electronic interactions between different groups in {[}Ru((6)-C16H16)(NH3)(3)](2+). (AU)

• FAPESP's process: 15/15176-2 - How to tune the Ru-NO coordination bond: insight from Kohn-Sham molecular orbital theory and energy decomposition analyses
• Grantee: Renato Pereira Orenha
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• FAPESP's process: 11/20351-7 - Computational study of ruthenium-nitosyl compounds
• Grantee: Renato Pereira Orenha
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 08/02677-0 - Computational Study of the interaction between HIV-1 reverse transcriptase non-nucleoside inhibitors with amino acids of the inhibitory site
• Grantee: Sergio Emanuel Galembeck
• Support Opportunities: Regular Research Grants