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Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands.
Osterloh, W Ryan; Galindo, Gabriel; Yates, Michelle J; Van Caemelbecke, Eric; Kadish, Karl M.
Afiliação
  • Osterloh WR; Department of Chemistry , University of Houston , Houston , Texas 77204-5003 , United States.
  • Galindo G; Department of Chemistry , Houston Baptist University , 7502 Fondren Road , Houston , Texas 77074-3298 , United States.
  • Yates MJ; Department of Chemistry , University of Houston , Houston , Texas 77204-5003 , United States.
  • Van Caemelbecke E; Department of Chemistry , Houston Baptist University , 7502 Fondren Road , Houston , Texas 77074-3298 , United States.
  • Kadish KM; Department of Chemistry , University of Houston , Houston , Texas 77204-5003 , United States.
Inorg Chem ; 59(1): 584-594, 2020 Jan 06.
Article em En | MEDLINE | ID: mdl-31876147
A series of water-soluble Ru25+ complexes of the type Ru2(O2CCH3)3(L)Cl where L = 2,3,4,5,6-F5ap, 2,4,6-F3ap, 2-Fap, ap, 2-Meap, 2,6-Me2ap, or 2,4,6-Me3ap, where ap is the anilinopyridinate anion, have been characterized as to their structural and physicochemical properties in H2O and DMSO. Five of the newly synthesized complexes were structurally characterized, and the Ru-Cl bond lengths range from 2.477 to 2.544 Å while the Ru-Ru bond lengths range from 2.2838 to 2.2935 Å. The UV-vis spectra of each compound are characterized by three absorption bands in both H2O and DMSO, the intensity and position of which vary with both the type of bridging ligand and the solvent. The seven examined Ru25+ complexes exist as 1:1 electrolytes in water, and each undergoes a reversible one-electron reduction assigned to Ru25+/Ru24+ in both investigated solvents. A second irreversible reduction attributed to Ru24+/Ru23+ is also observed for each compound at more negative potentials in DMSO. A linear free energy relationship exists between the sum of the Hammett substituent constants (Σσ) on the ap-type bridging ligand and the wavenumber of an absorption band for the Ru25+ complexes. A linear relationship is also seen between Σσ and measured E1/2 values for the Ru25+/Ru24+ process in water containing 0.1 M KCl, but little to no effect is seen between the specific bridging ligand and the structural features of the investigated compounds.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2020 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2020 Tipo de documento: Article