CO release by redox stimuli and HSA interaction: Planning new CORMs based on μ-oxo triruthenium carbonyl clusters

Author(s)

da Silva, Amanda Batista ; dos Santos, Nicolle A. P. ; Bertoloni, Renan Ribeiro ; de Oliveira-Filho, Antonio Gustavo Sampaio ; Nikolaou, Sofia

• Document type: Journal article
• Source: Polyhedron; v. 278, p. 9-pg., 2025-08-01.

Abstract

Hydrogen peroxide promoted the release of carbon monoxide through the oxidation of the [Ru3O (CH3COO)6(L)2CO]0 complexes (L = pyridine (1a), dimethylpyrazine (2a) and 4-tert-butylpyridine (3a)). For 1a, a two-step reaction was observed in acetonitrile, with pseudo-first order rate constants kobs1 = (10.9 +/- 2.9) x 10-3 s-1 and k2 = (11.8 +/- 0.8) x 10-4 s-1, assigned to the oxidation reaction RuIII,III,II/RuIII,III,III followed by the substitution of the coordinated CO by a solvent molecule. In acetate buffer, only one-step was observable. Comparison of the reaction rate of three related clusters suggested a dependence of the rate constants with the basicity of the ligands. The 4-tert-butylpyridine ligand increases the oxidative-induced CO release, since sigma-donation of electronic density by the more basic ligand facilitates the oxidation of the Ru(II) ion to Ru(III). We also addressed the possibility of interaction with a relevant biological target, using 1a as example. It is suggested that 1a interacts with human serum albumin (HSA) by the static mechanism, while the interaction of [Ru3O (CH3COO)6(pyridine)2H2O]+ (1b), the reaction product of 1a oxidation, also has a contribution from the dynamic mechanism. This implies that weak interactions play a major role, since the labile point does not seem to favour adduct formation by coordinative bonding. (AU)

• FAPESP's process: 21/14279-3 - Study of the orthometallation of phenanthrolines with trinuclear ruthenium acetates
• Grantee: Nicolle Azevedo Portela dos Santos
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis
• Grantee: Roberto Manuel Torresi
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 23/10722-5 - Computational design of bioinspired transition metal-based catalysts for H2 generation
• Grantee: Renan Ribeiro Bertoloni
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 22/03478-8 - Reactivity of polynuclear ruthenium compounds with potential biological application
• Grantee: Sofia Nikolaou
• Support Opportunities: Regular Research Grants
• FAPESP's process: 21/02802-3 - Study of redox reactivity and release of nitric oxide and carbon monoxide in trinuclear ruthenium carboxylates
• Grantee: Amanda Batista Silva
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 23/08615-6 - Reactivity and biological properties of asymmetric ruthenium trinuclear complexes with imidazole ligands
• Grantee: Amanda Batista Silva
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)