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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

How does the total charge and isomerism influence the Ru-NO ammine complexes?

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Author(s):
Orenha, Renato Pereira [1] ; Tfouni, Elia [1] ; Galembeck, Sergio Emanuel [1]
Total Authors: 3
Affiliation:
[1] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ribeirao Preto, SP - Brazil
Total Affiliations: 1
Document type: Journal article
Source: Physical Chemistry Chemical Physics; v. 20, n. 19, p. 13348-13356, MAY 21 2018.
Web of Science Citations: 2
Abstract

Nitric oxide plays an important role in several physiological processes. This study investigates model ruthenium ammine coordination compounds to control NO bioavailability: cis-{[}RuCl(NO)(NH3)(4)](+) (1(+)), cis-{[}RuCl(NO)(NH3)(4)](2+) (1(2+)), cis-{[}RuCl(NO)(NH3)(4)](3+) (1(3+)), trans-{[}RuCl(NO)(NH3)(4)](+) (2(+)), trans-{[}RuCl(NO)(NH3)(4)](2+) (2(2+)), trans-{[}RuCl(NO)(NH3)(4)](3+) (2(3+)), {[}Ru(NO)(NH3)(5)](+) (3(+)), {[}Ru(NO)(NH3)(5)](2+) (3(2+)), and {[}Ru(NO)(NH3)(5)](3+) (3(3+)). We employed natural population analysis (NPA) atomic charges (q(NPA)) and the LUMO to identify the main reduction sites in the complexes 1, 2 and 3. For example, in the transformations 1(2+) 1(+), 2(2+) 2(+), and 3(3+) 3(2+), the main reduction site was a NO {*} orbital, which accounted for the lower electron density of the Ru-NO bond critical point (BCP) in 1(+), 2(+), and 3(2+) than 1(2+), 2(2+), and 3(3+), respectively, as shown by the quantum theory of atoms in molecules (QTAIM). The QTAIM method indicated that the electron density was larger in Ru-NO BCP due to the Cl negative cis- and trans-influence in 1(2+) and 2(2+), respectively, as compared with the NH3 influence in 3(3+). Compared to trans-Cl-Ru-NO in 2(2+), the interacting quantum atoms method demonstrated that cis-Cl-Ru-NO in 1(2+) displayed (i) a larger repulsive electrostatic energy, which agreed with q(NPA), and (ii) a less negative exchange-correlation energy between Ru and the NO nitrogen atom, which agreed with topological analyses performed by the QTAIM method. Thus, the combination of topological and energy decomposition analyses allowed the mechanism behind the Ru-NO bond to be revealed regarding the influence of the total charge and the relative position of the ligands. (AU)

FAPESP's process: 11/20351-7 - Computational study of ruthenium-nitosyl compounds
Grantee:Renato Pereira Orenha
Support Opportunities: Scholarships in Brazil - 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 Opportunities: Regular Research 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 Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
FAPESP's process: 06/53266-4 - Chemistry, photochemistry and biological applications of ruthenium complexes with nitric oxide and related species. From solution to materials
Grantee:Elia Tfouni
Support Opportunities: Research Projects - Thematic Grants
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 Opportunities: BIOTA-FAPESP Program - Thematic Grants