Steric Ligand Effects of Six Bidentate Bipyridyl Ligands

Carol A. Bessel, Joseph A. Margarucci, J. Henry Acquaye, Robert S. Rubino, Janet Crandall, Alan J. Jircitano, Kenneth J. Takeuchi

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66 Scopus citations

Abstract

The synthesis and characterization of a series of [Ru(H2O)(N-N)(trpy)]2+ complexes (where N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 2,9-dimethyl-1,10-phenanthroline (2,9-Me2phen), 2,2′-biquinoline (biq), and 6,6′-dichloro-2,2′-bipyridine (6,6′-Cl2bpy), and trpy = 2,2′: 6′,2″-terpyridine) are described. The rate constants for ligand substitution of the aqua ligand for acetonitrile were determined for the [Ru(H2O) (N-N) (trpy)]2+ complexes as well as for a series of [Ru(H2O)(bpy)2(PR3)]2+ complexes in pH = 2.2 HNO3/NaNO3 (μ = 0.1) solution at 25 °C. The electronic (E) and steric (S) properties of the phopshine ligands in the [Ru(H2O)(bpy)2(PR3)]2+ complexes correlated well with the rate constants for ligand substitution (kls) using the relationship In kls = aE + bS + c (where a–c are constants which were determined by linear regression analyses). The equation for the [Ru(H2O)(bpy)2(PR3)]2+ complexes was used to calculate the cone angles of the six bidentate bipyridyl ligands (N-N). These cone angles represent the first quantitative estimates of steric ligand effects for bidentate bipyridyl ligands.

Original languageEnglish (US)
Pages (from-to)5779-5784
Number of pages6
JournalInorganic chemistry
Volume32
Issue number25
DOIs
StatePublished - Jan 1 1993

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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