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Thermodynamics of Axial Substitution and Kinetics of Reactions with Amino Acids for the Paddlewheel Complex Tetrakis(acetato)chloridodiruthenium(II,III).
MedLine Citation:
PMID:  22656370     Owner:  NLM     Status:  Publisher    
The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.
Rodrigo L S R Santos; Rudi van Eldik; Denise de Oliveira Silva
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-6-1
Journal Detail:
Title:  Inorganic chemistry     Volume:  -     ISSN:  1520-510X     ISO Abbreviation:  -     Publication Date:  2012 Jun 
Date Detail:
Created Date:  2012-6-4     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo , Av. Prof. Lineu Prestes, 748, CEP 05508-000, São Paulo, SP, Brazil.
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