Nature of the Ru-NO Coordination Bond: Kohn-Sham Molecular Orbital and Energy Decomposition Analysis

Author(s)

Orenha, Renato P. ; Rocha, Marcus V. J. ; Poater, Jordi ; Galembeck, Sergio E. ; Bickelhaupt, F. Matthias

• Document type: Journal article
• Source: CHEMISTRYOPEN; v. 6, n. 3, p. 410-416, JUN 2017.
• Web of Science Citations: 7

Abstract

We have analyzed structure, stability, and Ru-NO bonding of the trans-{[}RuCl(NO)(NH3)(4)](2+) complex by using relativistic density functional theory. First, we focus on the bond dissociation energies associated with the three canonical dissociation modes leading to {[}RuCl(NH3)(4)](+)+NO+, {[}RuCl(NH3)(4)](2+)+NO, and {[}RuCl(NH3)(4)](3+)+NO-. The main objective is to understand the Ru-NO+ bonding mechanism in the conceptual framework of Kohn-Sham molecular orbital theory in combination with a quantitative energy decomposition analysis. In our analyses, we have addressed the importance of the synergism between Ru-NO+ sigma-donation and pi-backdonation as well as the so-called negative trans influence of the Cl- ligand on the Ru-NO bond. For completeness, the Ru-NO+ bonding mechanism is compared with that of the corresponding Ru-CO bond. (AU)

• FAPESP's process: 14/50265-3 - Distribution and metabolism of natural and synthetic xenobiotics: from the comprehension of reactional process to tissue imaging generation
• Grantee: Norberto Peporine Lopes
• Support type: BIOTA-FAPESP Program - Thematic Grants
• 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 type: Scholarships abroad - Research Internship - 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 type: Regular Research Grants
• FAPESP's process: 11/20351-7 - Computational study of ruthenium-nitosyl compounds
• Grantee: Renato Pereira Orenha
• Support type: Scholarships in Brazil - Doctorate (Direct)