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Kinetic-mechanistic studies of ruthenium macrocyclic complexes formation as potential donors and scavengers of nitric oxide and correlated species

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Abstract

In this paper, the mechanisms of reactions involving complexes with tetraazamacrocyclic (mac) ligands against nitrosyl ligands in an aqueous medium were explored, with emphasis on reactivity to nitric oxide (NO) and analog species, like nitrite ion (NO2−). The reactions between [RuCl(OH2)(mac)]2+ with NO and [RuCl(OH)(mac)]2+ with NO2− were performed in an aqueous solution within pH 1 or 7, and the rate constants (k) and the thermodynamic parameters (∆H#, ∆S#) of activation were determined. The reaction between NO and the complex with cyclen is faster than that with the complex with cyclam. However, the reaction of the cyclen complex with NO2− is slower than NO. This research provides detailed reaction kinetics and thermodynamic activation parameters for these interactions for the first time. In addition, the redox processes of coordinated NO− and NO2− ligands to ruthenium were evaluated and the electrochemical release of NO from nitrosyl compounds upon electrochemical potential application. Our findings bring significant contributions in elucidating mechanisms related to NO capture both in vitro and in vivo.

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Acknowledgements

The authors thank the Brazilian agencies CNPq and CAPES for their financial support.

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Authors and Affiliations

  1. Departamento de Química Geral e Inorgânica, Instituto de Química, Universidade Federal da Bahia, Campus Universitário de Ondina, Rua Barão de Jeremoabo, s/n, Salvador, BA, 40170-115, Brazil

    Juliana Guerreiro Cezar, Tamires Mariel Muniz Milhazes & Kleber Queiroz Ferreira

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JGC, TMMM and KQF wrote the main manuscript text and TMMM prepared all figures. JGC and KQF performed the kinetic experiments. All authors reviewed the manuscript

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Correspondence to Kleber Queiroz Ferreira.

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Cezar, J.G., Milhazes, T.M.M. & Ferreira, K.Q. Kinetic-mechanistic studies of ruthenium macrocyclic complexes formation as potential donors and scavengers of nitric oxide and correlated species. Transit Met Chem (2024). https://doi.org/10.1007/s11243-024-00575-w

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