Tracking the role oftrans-ligands in ruthenium-NO bond lability: computational insight

Author(s)

Orenha, Renato Pereira ^[1] ; Guerra Silva, Graziele Cappato ^[1] ; de Lima Batista, Ana Paula ^[2] ; Sampaio de Oliveira Filho, Antonio Gustavo ^[2] ; Morgon, Nelson Henrique ^[3] ; da Silva, Vanessa Borges ^[1] ; Pereira Furtado, Saulo Samuel ^[1] ; Caramori, Giovanni Finoto ^[4] ; Piotrowski, Mauricio Jeomar ^[5] ; Tame Parreira, Renato Luis ^[1]

Affiliation

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

^[2] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ribeirao Preto - Brazil

^[3] Univ Estadual Campinas, Inst Quim, CP 6154, BR-13083970 Campinas, SP - Brazil

^[4] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

^[5] Univ Fed Pelotas, Dept Phys, POB 354, Pelotas, RS - Brazil

• Document type: Journal article
• Source: NEW JOURNAL OF CHEMISTRY; v. 44, n. 27, p. 11448-11456, JUL 21 2020.
• Web of Science Citations: 0

Abstract

Nitric oxide (NO) is an important endogenously produced molecule. Ruthenium-NO tetraamine complexes appear as model structures to investigate the control of nitric oxide bioavailability. NO release typically occurs through thetrans-{[}Ru-II(NH3)(4)L-trans(NO+)](3+/2+)+ e(-)-> trans-{[}Ru-II(NH3)(4)L-trans(NO0)](2+/+)reduction reaction, followed by thetrans-{[}Ru-II(NH3)(4)L-trans(NO0)](2+/+)+ H2O -> trans-{[}Ru-II(NH3)(4)L-trans(H2O)](2+/+)+ NO(0)hydrolysis reaction. The choice of the NOtransligand, L-trans, is fundamental to control the Ru-NO bond stability. Here, the nature and charge influences of L(trans)were evaluated considering the following ligands L-trans= sigma-donors (NH(3)and H-), pi-donors (H2O and NH2-), and pi-donors and pi-acceptors (CO and CN-) through the ZORA-BP86/TZ2P computational model. Energy Decomposition Analysis in conjunction with the Natural Orbitals for Chemical Valence methodology (EDA-NOCV) showed that molecules with L-trans= H2O and NH(2)(-)promoted larger Ru-NO stabilization than complexes with L-trans= NH(3)and H-, respectively, mainly due to the interaction orbital energy (Delta E-oi). The opposite trend was observed in compounds with L-trans= CO and CN(-)compared to structures with L-trans= H2O and NH2-. The study of the charge distribution, performed using the Voronoi Deformation Density (VDD) method, and the topological analysis of the electron density, realized using the Quantum Theory of Atoms in Molecules (QTAIM), on the investigated complexes indicated that L(trans)with negative charge promoted, in general, predominantly a decrease of the electron flux in the L-trans(sigma) -> Ru(d(sigma){*}) <- NO(sigma) process. (AU)

• 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: 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
• 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: 15/11714-0 - Reactivity, transformation, fixation, and spectroscopy of systems involving CO2
• Grantee: Antonio Gustavo Sampaio de Oliveira Filho
• Support Opportunities: Regular Research Grants
• 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: 17/18238-4 - Catalytic C-H activation reactions: computational study aiming atom efficiency in CO2 fixation
• Grantee: Ana Paula de Lima Batista
• Support Opportunities: Scholarships in Brazil - Post-Doctoral