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 (H(2)L), in its deprotonated form, a new mononuclear ruthenium(III) complex [Et(4)N][RuL(2)] x H(2)O (1) has been synthesized. Structural analysis reveals that the RuN(6) coordination comprises four deprotonated amide-N 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/CH(2)Cl(2) 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, [RuL(2)] x H(2)O (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 approximately 1400 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 pi-cation radical leads to an effectively S = 0 ground state ((1)H NMR spectra in CDCl(3) solution).