Tuning the hydrolytic properties of half-sandwich-type organometallic cations in aqueous solution

Linda Bíró, Attila J. Godó, Zsolt Bihari, Eugenio Garribba, P. Buglyó

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Hydrolysis of half-sandwich-type platinum metal cations with the general formula [M(η6-arene)(H2O)3]2+ {M = Ru, Os; η6-arene = benzene, toluene, 1-methyl-4- isopropylbenzene (p-cym), or 1,3,5-triisopropylbenzene (tri-iPr)} or [Ir(η5-Cp*)(H2O)3]2+ (Cp* = pentamethylcyclopentadienyl anion) was studied in aqueous solution in the presence of 0.20 M KNO3 or KCl as a background electrolyte to explore the effects of the type of metal ion, the moderately coordinating monodentate chloride ion, and the electron-donating ability of the arene ligand. Replacement of Ru by Os enhances the formation of the biologically less-active, triple hydroxido-bridged dimer, [{M(η6-arene)} 22-OH)3]+, whereas in the presence of Cl- complete hydrolysis is suppressed owing to the formation of various chlorido and mixed chlorido/hydroxido species as intermediates. A linear relationship was found between the stability constants of the [{Ru(η6-arene)}22-OH) 3]+ complexes in the presence of arenes with different electron-donating abilities and various atomic and molecular parameters of the corresponding [Ru(η6-arene)(H2O)3] 2+ cations; the triisopropylbenzene derivative was the most resistant to hydrolysis. The results of this study may help in rationalizing the bioactivity of anticancer half-sandwich metal complexes and can contribute to the rational design of metal compounds with increased biological activity. The hydrolytic properties of half-sandwich [M(η6-arene)(H 2O)3]2+ (M = Ru, Os; η6-arene = benzene, toluene, 1-methyl-4-isopropylbenzene, 1,3,5-triisopropylbenzene) or [Ir(η5-Cp*)(H2O)3]2+ (Cp* = pentamethylcyclopentadienyl) cations can be tuned by the proper selection of the arene system and by modification of the metal ion to make them more resistant to hydrolysis.

Original languageEnglish
Pages (from-to)3090-3100
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number17
DOIs
Publication statusPublished - Jun 2013

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Organometallics
Cations
Hydrolysis
Tuning
Toluene
Bioactivity
Benzene
Metal ions
Platinum metals
Electrons
Coordination Complexes
Dimers
Electrolytes
Anions
Chlorides
Metals
Ions
Ligands
Derivatives
cumene

Keywords

  • Half-sandwich complexes
  • Hydrolysis
  • Iridium
  • Osmium
  • Ruthenium
  • Stability constant

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Tuning the hydrolytic properties of half-sandwich-type organometallic cations in aqueous solution. / Bíró, Linda; Godó, Attila J.; Bihari, Zsolt; Garribba, Eugenio; Buglyó, P.

In: European Journal of Inorganic Chemistry, No. 17, 06.2013, p. 3090-3100.

Research output: Contribution to journalArticle

Bíró, Linda ; Godó, Attila J. ; Bihari, Zsolt ; Garribba, Eugenio ; Buglyó, P. / Tuning the hydrolytic properties of half-sandwich-type organometallic cations in aqueous solution. In: European Journal of Inorganic Chemistry. 2013 ; No. 17. pp. 3090-3100.
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