Structural and solution equilibrium studies on half-sandwich organorhodium complexes of (N,N) donor bidentate ligands

János P. Mészáros, Orsolya Dömötör, Carmen M. Hackl, Alexander Roller, Bernhard K. Keppler, Wolfgang Kandioller, Éva A. Enyedy

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Complex formation equilibrium processes of [Rh(η5-C5Me5)(H2O)3]2+ with N,N′-dimethylethylenediamine (dmen), N,N,N′,N′-tetramethylethylenediamine (tmeda), 2-picolylamine (pin) and 1,10-phenanthroline (phen) were studied in aqueous solution by 1H NMR spectroscopy, UV-vis spectrophotometry and pH-potentiometry. Formation and deprotonation of [Rh(η5-C5Me5)(L)(H2O)]2+ complexes and exchange process of the aqua to chlorido ligand were characterized in addition to single-crystal X-ray diffraction analysis of [Rh(η5-C5Me5)(L)(Cl)]+ complexes (L = dmen, tmeda and pin). Formation of complexes with significantly high stability was found except tmeda due to the sterical hindrance between the methyl groups of the chelating ligand and the arenyl ring resulting in an increased methyl group-ring plane torsion angle. [Rh(η5-C5Me5)(L)(H2O)]2+ complexes of dmen, pin, phen predominate at pH 7.4 without decomposition even in the micromolar concentration range. The complexes were characterized by relatively high chloride affinity and a strong correlation was obtained between the log K′ (H2O/Cl-) and pKa of [Rh(η5-C5Me5)(L)(H2O)]2+ constants for a series of (O,O), (O,N) and (N,N)-chelated complexes. For this set of 12 complexes a relationship between log K′ (H2O/Cl-) values and certain crystallographic parameters was found using multiple linear regression approach. DNA binding of these complexes was also monitored and compared by ultrafiltration and fluorimetry.

Original languageEnglish
Pages (from-to)11174-11184
Number of pages11
JournalNew Journal of Chemistry
Volume42
Issue number13
DOIs
Publication statusPublished - Jan 1 2018

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

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