title: Chemical, electrochemical, and photochemical catalytic oxidation of water to dioxygen with mononuclear ruthenium complexes.
abstract: Four new Ru(II)-Cl and Ru(II)-H(2)O complexes containing the meridional 2,2':6',2"-terpyridine (trpy) ligand and the chelating 2-(5-phenyl-1H-pyrazol-3-yl)pyridine (H3p) ligand of general formula in- and out-[Ru(II) (trpy)(H3p)(X)](n+) (X=Cl, n=1; X=H(2)O, n=2) have been prepared, isolated and thoroughly characterized both in solution and in the solid state. In solution, all the complexes are characterized spectroscopically by UV/Vis and NMR, and their redox properties investigated by means of cyclic voltammetry, square wave voltammetry, and coulometry. In the solid state, monocrystal X-ray diffraction analysis was carried out for the in and out Ru-Cl complexes. The capacity of the Ru-aqua complexes to act as water oxidation catalysts (WOCs) was also investigated chemically, electrochemically, and photochemically. The performance of these complexes has also been compared to two previously described complexes of general formula in- and out-[Ru(II)(trpy)(Hbpp)(H(2)O)](2+) (Hbpp is 2,2'-(1H-pyrazole-3,5-diyl)dipyridine)), the capacity of which as WOCs had not been previously described.
authors.affiliation: Catalan Institute of Chemical Research (ICIQ), Av. Paisos Catalans 16, 43007 Tarragona, Spain.
authors.forename: Stephan
authors.initials: S
authors.lastname: Roeser
authors.forename: Pau
authors.initials: P
authors.lastname: Farràs
authors.forename: Fernando
authors.initials: F
authors.lastname: Bozoglian
authors.forename: Marta
authors.initials: M
authors.lastname: Martínez-Belmonte
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet
mesh_terms: D002384:Catalysis; D004563:Electrochemistry; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D011720:Pyrazoles / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D009942:Organometallic Compounds; D011720:Pyrazoles; D011725:Pyridines; D014867:Water; D012428:Ruthenium; D010100:Oxygen