Inorganic Chemistry, Vol.42, No.20, 6497-6502, 2003
Synthesis and characterization of low-spin and cation radical complexes of ruthenium(III) of a tridentate pyridine bis-amide ligand
Using a tridentate bis-amide ligand 2,6-bis(N-phenylcarbamoyl)pyridine (H2L), in its deprotonated form, a new mononuclear ruthenium(III) complex [Et4N][RuL2].H2O (1) has been synthesized. Structural analysis reveals that the RuN6 coordination comprises four deprotonated ani species in the equatorial plane and two pyridine-N donors in the axial positions, imparting a tetragonally compressed octahedron around Ru. To the best of our knowledge, this is the first time that a ruthenium(III) complex coordinated solely by two tridentate deprotonated peptide ligands has been synthesized and structurally characterized. When examined by cyclic voltammetry, complex 1 displays in MeCN/CH2Cl2 solution three chemically/electrochemically reversible redox processes: a metal-centered reductive Ru-III-Ru-II couple (E-1/2 = -0.84/-0.89 V vs SCE) and two ligand-centered oxidative responses (E-1/2 = 0.59/0.60 and 1.05/1.05 V vs SCE). Isolation of a dark blue one-electron oxidized counterpart of 1, [RuL2].H2O (2), has also been readily achieved. The complexes have been characterized by analytical, solution electrical conductivity, IR, electronic absorption and EPR spectroscopy, and temperature-dependent magnetic susceptibility measurements, For complex 1, a weak and broad transition within the t(2g) level has been identified at similar to1400 nm and supported by EPR spectral analysis (S = 1/2). Temperature-dependent magnetic susceptibility data provide unambiguous evidence that in 2 strong antiferromagnetic coupling of the S = 1/2 ruthenium atom with the S = 1/2 ligand :T-cation radical leads to an effectively S = 0 ground state (H-1 NMR spectra in CDCl3 solution).