| Texto completo | |
| Autor(es): |
Goncalves, Felipe de Santis
;
Macedo, Lucyano J. A.
;
Souza, Maykon L.
;
Lehnert, Nicolai
;
Crespilho, Frank N.
;
Roveda Jr, Antonio C.
;
Cardoso, Daniel R.
Número total de Autores: 7
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Inorganic Chemistry; v. 63, n. 45, p. 10-pg., 2024-10-30. |
| Resumo | |
Ruthenium(II) tetraamine nitrosyl complexes with N-heterocyclic ligands are known for their potential as nitric oxide (NO center dot) donors, capable of releasing NO center dot through either direct photodissociation or one-electron reduction of the Ru(II)NO+ center. This study delivers a novel insight into the one-electron reduction mechanism for the model complex trans-[RuII(NO)(NH3)4(py)]3+ (RuNOpy, py = pyridine) in phosphate buffer solution (pH 7.4). In situ FT-IR spectroelectrochemistry reveals that the pyridine ligand is readily released upon one-electron reduction of the nitrosyl complex, a finding supported by nuclear magnetic resonance spectroscopy (1H NMR) and electrochemistry coupled to mass spectrometry (EC-MS), which detect free pyridine in solution. However, direct evidence of NO center dot release from RuNOpy as the primary step following reduction was not observed. Interestingly, FT-IR results indicate that the isomers of the nitrosyl complex, cis-[Ru(NO)(NH3)4(OH)]+ and trans-[Ru(NO)(NH3)4(OH)]+, are formed following reduction and pyridine labilization, initiating an outer-sphere electron transfer process that triggers a chain electron transfer reaction. Finally, nitric oxide is liberated as an end product, arising from the reduction of the hydroxyl isomer complexes cis-[Ru(NO)(NH3)4(OH)]2+ and trans-[Ru(NO)(NH3)4(OH)]2+. This study provides new insights into the reduction mechanism and transformation pathways of ruthenium nitrosyl complexes, contributing to our understanding of their potential as NO center dot donors. (AU) | |
| Processo FAPESP: | 17/01189-0 - Novel aging: tecnologias e soluções para fabricar novos produtos lácteos para um envelhecimento saudável |
| Beneficiário: | Daniel Rodrigues Cardoso |
| Modalidade de apoio: | Auxílio à Pesquisa - Temático |