Formation and release of NO from ruthenium nitrosyl ammine complexes [Ru(NH3)5(NO)]²+/³+ in aqueous solution: a theoretical investigation

Gabriel Libânio Silva Rodrigues; Willian Ricardo Rocha

Please use this identifier to cite or link to this item: http://hdl.handle.net/1843/50315

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DC Field	Value	Language
dc.creator	Gabriel Libânio Silva Rodrigues	pt_BR
dc.creator	Willian Ricardo Rocha	pt_BR
dc.date.accessioned	2023-02-23T14:50:59Z	-
dc.date.available	2023-02-23T14:50:59Z	-
dc.date.issued	2016	-
dc.citation.volume	120	pt_BR
dc.citation.issue	45	pt_BR
dc.citation.spage	11821	pt_BR
dc.citation.epage	11833	pt_BR
dc.identifier.doi	https://doi.org/10.1021/acs.jpcb.6b08813	pt_BR
dc.identifier.issn	15205207	pt_BR
dc.identifier.uri	http://hdl.handle.net/1843/50315	-
dc.description.resumo	In this article, density functional theory in conjunction with Monte Carlo statistical mechanical simulation was used to investigate the electronic structure, reduction potential, solvation, and solvent effects on the electronic spectra of nitrosyl ammine complexes using [Ru(NH3)5(NO)]²+/²+ as model compounds. In addition, ligand exchange reactions with solvent water molecules were also investigated. It is shown that the complexes are involved in strong hydrogen bonds in aqueous solution, with mean average energies of −13.5 ± 0.4 and −22.4 ± 0.4 kcal mol–1 for Ru(II) and Ru(III), respectively. Interestingly, for all the complexes studied, the NO ligand is not involved in hydrogen bonding interactions in aqueous solution. These strong hydrogen bonds are responsible for the high stability of these complexes in aqueous solution, showing formation constants Kf greater than 1021. The complex [Ru(NH3)5(NO)]3+ can easily be reduced by biological reducing agents in both the singlet and triplet states; however, the reduction is easier in the triplet state, which has a positive reduction potential of 1.70 V. The formation of [Ru(NH3)5(NO)]3+ in its most stable singlet state may take place through at least two singlet–triplet surface crossings leading to nonadiabatic effects. The existence of the minimum-energy crossing points makes the release of NO from the triplet state more favorable, with an activation energy almost seven times lower (∼6 kcal mol–1).	pt_BR
dc.description.sponsorship	CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico	pt_BR
dc.description.sponsorship	FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais	pt_BR
dc.description.sponsorship	INCT – Instituto nacional de ciência e tecnologia (Antigo Instituto do Milênio)	pt_BR
dc.language	eng	pt_BR
dc.publisher	Universidade Federal de Minas Gerais	pt_BR
dc.publisher.country	Brasil	pt_BR
dc.publisher.department	ICX - DEPARTAMENTO DE QUÍMICA	pt_BR
dc.publisher.initials	UFMG	pt_BR
dc.rights	Acesso Restrito	pt_BR
dc.subject	Ligands	pt_BR
dc.subject	Molecules	pt_BR
dc.subject	Nitrosyls	pt_BR
dc.subject	Quantum mechanics	pt_BR
dc.subject	Solvents	pt_BR
dc.subject.other	Físico-química	pt_BR
dc.subject.other	Moléculas	pt_BR
dc.subject.other	Mecânica quântica	pt_BR
dc.subject.other	Solventes	pt_BR
dc.subject.other	Óxido nítrico	pt_BR
dc.subject.other	Funcionais de densidade	pt_BR
dc.subject.other	Complexos metálicos de transição	pt_BR
dc.subject.other	Compostos de rutênio	pt_BR
dc.subject.other	Método de Monte Carlo	pt_BR
dc.title	Formation and release of NO from ruthenium nitrosyl ammine complexes [Ru(NH3)5(NO)]²+/³+ in aqueous solution: a theoretical investigation	pt_BR
dc.type	Artigo de Periódico	pt_BR
dc.url.externa	https://pubs.acs.org/doi/10.1021/acs.jpcb.6b08813	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-6580-3336	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-0025-2158	pt_BR
Appears in Collections:	Artigo de Periódico

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