title: 3d element complexes of pentadentate bipyridine-pyridine-based ligand scaffolds: structures and photocatalytic activities.
abstract: The synthesis of the two penta-pyridyl type ligands pyridine-2,6-diylbis(dipyridin-2-ylmethanol) (PPy, 1) and bis-2,2''-bipyridine-6-yl(pyridine-2-yl)methanol (aPPy, 2) is described. Both ligands coordinate rapidly to the 3d element cations Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), thereby yielding complexes of the general composition [MBr(1)](+) and [MBr(2)](+), respectively. Further, the X-ray structures of selected complexes with ligands 1 and 2 are described. They show metal center dependent structural features and complexes with 2 exhibiting distinctly distorted octahedral geometries. Moreover, photocatalytic water reduction with [Co(II)Br(PPy)]Br (1c) and [Co(II)Br(aPPy)]Br (2c) as water reducing catalysts (WRC) was investigated. Both complexes showed catalytic activity in water when in presence of ascorbic acid as sacrificial electron donor and [Re(py)(bpy)(CO)3](+) (3) as photosensitizer (PS). Turnover numbers, TONs (H2/Co), up to 11,000 were achieved. Complex 2c was more active than 1c, whereas none of the other complexes showed any activity.
authors: Institute of Inorganic Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland.
authors: Cyril
authors: C
authors: Bachmann
authors: Miguel
authors: M
authors: Guttentag
authors: Bernhard
authors: B
authors: Spingler
authors: Roger
authors: R
authors: Alberto
mesh_terms: D002384:Catalysis; D008024:Ligands; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D055668:Photochemical Processes; D011725:Pyridines / Q000737:chemistry*
chemical_list: D008024:Ligands; D019216:Metals, Heavy; D009942:Organometallic Compounds; D011725:Pyridines