Characterisation of ternary complex formation between [Ru III(edta)]- and various bidentate ligands

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Abstract

Speciations of ruthenium(III)-edta complexes of bidentate (O, O) (N, O) and (S, O) donor type ligands were determined by pH-potentiometry and UV/Vis spectrophotometry in aqueous solution. Complexes of [RuIII(edtaH x)L]2- (x = 0, 1, 2 and 3) stoichiometry were only formed and the fully deprotonated species dominate at the physiological pH 7.4. Protonation occurs at the free carboxylate arms of edta; when x = 3 one of the coordination positions of the RuIII becomes free. Formation of protonated ternary complexes are more characteristic for ligands with (N, O) and (S, O) donor sets where the complex formation started (ligands with (N, O) donor set) or completed (ligands with (S, O) donor set) already at pH 2. In acidic conditions the stability order of the complexes follows the (O, O) <(N, O) <(S, O) sequence, which changes slightly for the physiological pH 7.4: (O, O) ≈ (N, O) <(S, O). The complexes formed were characterised also by LNT EPR spectroscopy. The kinetics of the ligand exchange between ternary complexes at pH 6 was found to be dissociative. The reaction rate follows basically the stability order: (O, O) <(N, O) <(S, O). No side reactions were found when the ligands replaced had (O, O) donor set; but formation of [RuIII(edta)(L1),(L2)] 3- was hypothesised in the case of ligands with (N, O) or (S, O) donor sets.

Original languageEnglish
Pages (from-to)1640-1647
Number of pages8
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume639
Issue number8-9
DOIs
Publication statusPublished - Jul 2013

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Ligands
Ruthenium
Protonation
Spectrophotometry
Stoichiometry
Reaction rates
Paramagnetic resonance
Spectroscopy
Kinetics

Keywords

  • Edta
  • Kinetics
  • Ruthenium(III) complexes
  • Speciation
  • Ternary complex formation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Characterisation of ternary complex formation between [Ru III(edta)]- and various bidentate ligands",
abstract = "Speciations of ruthenium(III)-edta complexes of bidentate (O, O) (N, O) and (S, O) donor type ligands were determined by pH-potentiometry and UV/Vis spectrophotometry in aqueous solution. Complexes of [RuIII(edtaH x)L]2- (x = 0, 1, 2 and 3) stoichiometry were only formed and the fully deprotonated species dominate at the physiological pH 7.4. Protonation occurs at the free carboxylate arms of edta; when x = 3 one of the coordination positions of the RuIII becomes free. Formation of protonated ternary complexes are more characteristic for ligands with (N, O) and (S, O) donor sets where the complex formation started (ligands with (N, O) donor set) or completed (ligands with (S, O) donor set) already at pH 2. In acidic conditions the stability order of the complexes follows the (O, O) <(N, O) <(S, O) sequence, which changes slightly for the physiological pH 7.4: (O, O) ≈ (N, O) <(S, O). The complexes formed were characterised also by LNT EPR spectroscopy. The kinetics of the ligand exchange between ternary complexes at pH 6 was found to be dissociative. The reaction rate follows basically the stability order: (O, O) <(N, O) <(S, O). No side reactions were found when the ligands replaced had (O, O) donor set; but formation of [RuIII(edta)(L1),(L2)] 3- was hypothesised in the case of ligands with (N, O) or (S, O) donor sets.",
keywords = "Edta, Kinetics, Ruthenium(III) complexes, Speciation, Ternary complex formation",
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TY - JOUR

T1 - Characterisation of ternary complex formation between [Ru III(edta)]- and various bidentate ligands

AU - Jakusch, T.

AU - Kiss, T.

PY - 2013/7

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N2 - Speciations of ruthenium(III)-edta complexes of bidentate (O, O) (N, O) and (S, O) donor type ligands were determined by pH-potentiometry and UV/Vis spectrophotometry in aqueous solution. Complexes of [RuIII(edtaH x)L]2- (x = 0, 1, 2 and 3) stoichiometry were only formed and the fully deprotonated species dominate at the physiological pH 7.4. Protonation occurs at the free carboxylate arms of edta; when x = 3 one of the coordination positions of the RuIII becomes free. Formation of protonated ternary complexes are more characteristic for ligands with (N, O) and (S, O) donor sets where the complex formation started (ligands with (N, O) donor set) or completed (ligands with (S, O) donor set) already at pH 2. In acidic conditions the stability order of the complexes follows the (O, O) <(N, O) <(S, O) sequence, which changes slightly for the physiological pH 7.4: (O, O) ≈ (N, O) <(S, O). The complexes formed were characterised also by LNT EPR spectroscopy. The kinetics of the ligand exchange between ternary complexes at pH 6 was found to be dissociative. The reaction rate follows basically the stability order: (O, O) <(N, O) <(S, O). No side reactions were found when the ligands replaced had (O, O) donor set; but formation of [RuIII(edta)(L1),(L2)] 3- was hypothesised in the case of ligands with (N, O) or (S, O) donor sets.

AB - Speciations of ruthenium(III)-edta complexes of bidentate (O, O) (N, O) and (S, O) donor type ligands were determined by pH-potentiometry and UV/Vis spectrophotometry in aqueous solution. Complexes of [RuIII(edtaH x)L]2- (x = 0, 1, 2 and 3) stoichiometry were only formed and the fully deprotonated species dominate at the physiological pH 7.4. Protonation occurs at the free carboxylate arms of edta; when x = 3 one of the coordination positions of the RuIII becomes free. Formation of protonated ternary complexes are more characteristic for ligands with (N, O) and (S, O) donor sets where the complex formation started (ligands with (N, O) donor set) or completed (ligands with (S, O) donor set) already at pH 2. In acidic conditions the stability order of the complexes follows the (O, O) <(N, O) <(S, O) sequence, which changes slightly for the physiological pH 7.4: (O, O) ≈ (N, O) <(S, O). The complexes formed were characterised also by LNT EPR spectroscopy. The kinetics of the ligand exchange between ternary complexes at pH 6 was found to be dissociative. The reaction rate follows basically the stability order: (O, O) <(N, O) <(S, O). No side reactions were found when the ligands replaced had (O, O) donor set; but formation of [RuIII(edta)(L1),(L2)] 3- was hypothesised in the case of ligands with (N, O) or (S, O) donor sets.

KW - Edta

KW - Kinetics

KW - Ruthenium(III) complexes

KW - Speciation

KW - Ternary complex formation

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SN - 0044-2313

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