Synthesis and Structure of Ruthenium(IV) Complexes Featuring N-Heterocyclic Ligands with an N-H Group as the Hydrogen-Bond Donor: Hydrogen Interactions in Solution and in the Solid State

The synthesis and characterization of novel ruthenium(IV) complexes [Ru(eta(3):eta(3)-C10H16)Cl2L] [L = 3-methylpyrazole (2b), 3,5-dimethylpyrazole (2c), 3-methy1-5-phenylpyrazole (2d), 2-(1H-pyrazol-5-yOphenol (2e), 6-azauracile (3), and 1H-indazol-3-ol (4)] are reported. Complex 2e is converted to the chelated complex [Ru(eta(3):eta(3)-C10H16)Cl(kappa(2)-N, O-2-(1H-pyrazol-3-yl)phenoxy)] (5) by treatment with an excess of NaOH. All of the ligands feature N-H, O-H, or C=O as the potential hydrogen-bonding group. The structures of complexes 2a-2c, 2e, 3, and 5 in the solid state have been determined by X-ray diffraction. Complexes 2a-2c and 3, which contain the pyrazole N-H group, exhibit intra- and intermolecular hydrogen bonds with chloride ligands [N-H center dot center dot center dot Cl distances (A): intramolecular, 2.30-2.78; intermolecular, 2.59-2.77]. Complexes 2e and 3 bearing respectively O-H and C=O groups also feature N-H center dot center dot center dot O interactions [intramolecular (2e), 2.27 angstrom; intermolecular (3), 2.00 angstrom] Chelated complex 5, lacking the O-H group, only shows an intramolecular N-H center dot center dot center dot Cl hydrogen bonding of 2.42 angstrom. The structure of complex 3, which turns out to be a dimer in the solid state through a double intermolecular N-H center dot center dot center dot O hydrogen bonding, has also been investigated in solution (CD2Cl2) by NMR diffusion studies. Diffusion-ordered spectroscopy experiments reveal an equilibrium between monomer and dimer species in solution whose extension depends on the temperature, concentration, and coordinating properties of the solvent. Preliminary catalytic studies show that complex 3 is highly active in the redox isomerization of the allylic alcohols in an aqueous medium under very mild reaction conditions (35 degrees C) and in the absence of a base.