Can the relative positions (cis-trans) of ligands really modulate the coordination of NO in ruthenium nitrosyl complexes?

Author(s)

Orenha, Renato Pereira ^[1] ; Silva, Graziele Cappato Guerra ^[1] ; Morgon, Nelson Henrique ^[2] ; Caramori, Giovanni Finoto ^[3] ; Parreira, Renato Luis Tame ^[1]

Affiliation

^[1] Univ Franca, Nucleo Pesquisas Ciencias Exatas & Tecnol, Franca, SP - Brazil

^[2] Univ Estadual Campinas, Inst Quim, CP 6154, BR-13083970 Campinas, SP - Brazil

^[3] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

• Document type: Journal article
• Source: NEW JOURNAL OF CHEMISTRY; v. 45, n. 3, p. 1658-1666, JAN 21 2021.
• Web of Science Citations: 0

Abstract

Nitric oxide is involved in a series of biological processes. Ruthenium tetraammine complexes are model structures to control the NO availability. The influence of ligands is critical to determine the Ru-NO bond stability. Herein, the ligands of different natures and charges, namely, sigma-donors (NH3 and H-), (ii) pi-donors (H2O and NH2-), and (iii) sigma-donors/pi-acceptors (CO and CN-) were evaluated relative to the effect promoted by same ligands not only in the cis position to the NO group, but also in the trans position to NO. The energy decomposition analysis shows linear Ru-NO+ and bent Ru-NO0 bonds in ruthenium tetraammine complexes independent of ligands in cis or trans positions with regard to the NO group. Overall, the substitution of one sigma-donor ligand with one pi-donor ligand in the cis position to the NO group not stabilized the Ru-NO bond. These substitutions involving ligands in the trans position to NO stabilized the Ru-NO bond. Complexes with sigma-donor/pi-acceptor ligands compared to compounds with pi-donor ligands in the cis or trans position to the NO group destabilized the Ru-NO bond. Charge distribution investigation realized from the Voronoi deformation density (VDD) method presents the Ru-NO bond more stabilized by negatively charged sigma-donor, pi-donor and sigma-donor/pi-acceptor ligands, in the cis or trans position to NO. These findings provide crucial information to the rational design of new NO storage-release systems with potential to deliver NO to desired targets in a controlled manner. (AU)

• FAPESP's process: 13/08293-7 - CCES - Center for Computational Engineering and Sciences
• Grantee: Munir Salomao Skaf
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 19/00543-0 - How modulate the Ruthenium-NO chemical bond from ligands of different nature?
• Grantee: Graziele Cappato Guerra Silva
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion
• Grantee: Renato Luis Tame Parreira
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 15/22338-9 - Study of the interaction between drugs and human serum albumin (HSA) based on computer simulation, DFT and TDDFT, experiments of electronic circular dichroism, ECD, and determination of the bond formation constant
• Grantee: Aguinaldo Robinson de Souza
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/24856-2 - The Mechanism of the Substitution Reaction of the Ligand Nitrosyl by Aqua in Ruthenium Coordination Compounds
• Grantee: Renato Pereira Orenha
• Support Opportunities: Scholarships in Brazil - Post-Doctoral