Kinetic and mechanistic studies on reactions of diruthenium(ii,iii) with biologically relevant reducing agentsElectronic supplementary information (ESI) available: Absorption spectra, ESI-MS data, and additional tables containing rate constants. See DOI: 10.1039/c3dt51763b

Diruthenium( ii , iii )-tetracarboxylates have shown promising anticancer properties as metallotherapeutics. On the basis of the role that bio-reducing agents may play on the mode of action of ruthenium-based anticancer drugs, we performed detailed kinetic studies on the reaction of ascorbic acid an...

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Main Authors: Santos, Rodrigo Luis Silva Ribeiro, van Eldik, Rudi, de Oliveira Silva, Denise
Format: Article
Language:English
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Summary:Diruthenium( ii , iii )-tetracarboxylates have shown promising anticancer properties as metallotherapeutics. On the basis of the role that bio-reducing agents may play on the mode of action of ruthenium-based anticancer drugs, we performed detailed kinetic studies on the reaction of ascorbic acid and glutathione with the [Ru 2 (RCOO) 4 ] + paddlewheel framework by using the non-drug, diaqua complex ion [Ru 2 (CH 3 COO) 4 (H 2 O) 2 ] + . In the presence of the reducing agents, the diaqua-Ru 2 species first undergo a ligand substitution reaction by which the axially-coordinated water is displaced by the reducing agent. In both cases, this reaction is followed by an intra-molecular electron transfer process during which the metal-metal center is reduced from Ru 2 5+ to Ru 2 4+ and the reducing agent is oxidized. Product analyses were performed with the application of ESI-MS and 1 H-NMR techniques. Rate and activation parameters are reported for the different reaction steps. Reactions of the paddlewheel complex [Ru 2 (CH 3 COO) 4 (H 2 O) 2 ] + with glutathione and ascorbic acid were studied. In the presence of these nucleophiles, the diaqua-Ru 2 species first undergo a ligand substitution reaction followed by an intra-molecular electron transfer process.
ISSN:1477-9226
1477-9234
DOI:10.1039/c3dt51763b