Half-sandwich complexes of ruthenium, osmium, rhodium and iridium with dl-methionine or S-methyl-l-cysteine

A solid state and solution equilibrium study

János Patalenszki, Linda Bíró, A. Bényei, Tereza Radosova Muchova, Jana Kasparkova, P. Buglyó

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

[(η6-p-cym)Ru(H2O)3]2+ binding strength of the thioether ligands dl-methionine (H2met+) or S-methyl-l-cysteine (H2mecys+) was studied with the combined use of pH-potentiometry, NMR and mass spectrometry in aqueous solution. Both ligands were found to form stable [(η6-p-cym)RuA]+ complexes with [S, NH2, COO-] coordination of the amino acids over a wide pH-range. A logβRuA value of 17.2(2) was obtained from NMR titrations for the met system by a competition reaction with hydroxide ions. Comparison of the [(η6-p-cym)Ru(H2O)3]2+ binding strength of the [O, O, O] (citrate), [O, N, O] (isoserine) and [S, N, O] (met) donor sets at pH = 7.4 reveals the exclusive formation of a [S, N, O] chelated metal complex. Synthesis and characterisation of [(η6-p-cym)Ru(L)]X, [(η6-p-cym)Os(L)]Cl or [(η5-Cp∗)M′(L)]Cl (L = mecys, dl-met, l-met; X = Cl, NO3, CF3SO3; M′ = Rh, Ir) complexes together with the molecular structures of the [(η6-p-cym)Ru(mecys)]NO3 (10) and [(η6-p-cym)Ru(met)]NO3 (11) obtained by the X-ray diffraction method are reported. Both tridentate ligands form chiral-at-metal complexes in which the configuration of the metal centre is determined by the ligands containing a stereogenic centre (αC) as well. Diffraction data indicate that 10 contains the RRuRαCSS stereoisomer while 11 consists of the RRuSαCRS and SRuRαCSS enantiomers in the lattice. Owing to the labile configuration of the thioether sulfurs epimerisation in both systems was detected and the ratio of the diastereomers was estimated. 11 together with [(η6-p-cym)Ru(l-met)]Cl (3), [(η5-Cp∗)Rh(dl-met)]Cl (7) and [(η5-Cp∗)Ir(dl-met)]Cl (9) were tested for their in vitro cytotoxicity using human-derived ovarian cancer lines (A2780) and showed no anti-proliferative activity in the concentration range (0-50 μM) studied. This journal is

Original languageEnglish
Pages (from-to)8094-8107
Number of pages14
JournalRSC Advances
Volume5
Issue number11
DOIs
Publication statusPublished - 2015

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Osmium
Iridium
Rhodium
Ruthenium
Methionine
Cysteine
Ligands
Coordination Complexes
Sulfides
Metal complexes
Nuclear magnetic resonance
Stereoisomerism
Enantiomers
Cytotoxicity
Titration
Sulfur
Citric Acid
Molecular structure
Mass spectrometry
Amino acids

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Half-sandwich complexes of ruthenium, osmium, rhodium and iridium with dl-methionine or S-methyl-l-cysteine : A solid state and solution equilibrium study. / Patalenszki, János; Bíró, Linda; Bényei, A.; Muchova, Tereza Radosova; Kasparkova, Jana; Buglyó, P.

In: RSC Advances, Vol. 5, No. 11, 2015, p. 8094-8107.

Research output: Contribution to journalArticle

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AU - Bíró, Linda

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