title: Water oxidation by mononuclear ruthenium complexes with TPA-based ligands.
abstract: The synthesis, characterization, and water oxidation activity of mononuclear ruthenium complexes with tris(2-pyridylmethyl)amine (TPA), tris(6-methyl-2-pyridylmethyl)amine (Me(3)TPA), and a new pentadentate ligand N,N-bis(2-pyridinylmethyl)-2,2'-bipyridine-6-methanamine (DPA-Bpy) have been described. The electrochemical properties of these mononuclear Ru complexes have been investigated by both experimental and computational methods. Using Ce(IV) as oxidant, stoichiometric oxidation of water by [Ru(TPA)(H(2)O)(2)](2+) was observed, while Ru(Me(3)TPA)(H(2)O)(2)](2+) has much less activity for water oxidation. Compared to [Ru(TPA)(H(2)O)(2)](2+) and [Ru(Me(3)TPA)(H(2)O)(2)](2+), [Ru(DPA-Bpy)(H(2)O)](2+) exhibited 20 times higher activity for water oxidation. This study demonstrates a new type of ligand scaffold to support water oxidation by mononuclear Ru complexes.
authors: Department of Chemistry, The University of Memphis, Memphis, Tennessee 38152, USA.
authors: Bhasker
authors: B
authors: Radaram
authors: Jeffrey A
authors: JA
authors: Ivie
authors: Wangkheimayum Marjit
authors: WM
authors: Singh
authors: Rafal M
authors: RM
authors: Grudzien
authors: Joseph H
authors: JH
authors: Reibenspies
authors: Charles Edwin
authors: CE
authors: Webster
authors: Xuan
authors: X
authors: Zhao
mesh_terms: D032701:Biomimetics / Q000379:methods*; D002563:Cerium / Q000737:chemistry; D018360:Crystallography, X-Ray; D004563:Electrochemistry / Q000379:methods*; D006859:Hydrogen / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis; D010083:Oxidants, Photochemical / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010788:Photosynthesis; D011725:Pyridines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010083:Oxidants, Photochemical; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; D014867:Water; D002563:Cerium; D012428:Ruthenium; D006859:Hydrogen; D010100:Oxygen