title: Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.
abstract: Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.
authors.affiliation: †Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Yuki
authors.affiliation: ‡Faculty of Pharmaceutical Sciences, Hoshi University, Ebara, Shinagawa-ku, Tokyo 142-8501, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Sakata
authors.affiliation: §Fuel Cell System Development Center, Toyota Motor Corporation, Mishuku, Susono, Shizuoka 410-1193, Japan.
authors.forename: Yoshifumi
authors.initials: Y
authors.lastname: Hirao
authors.affiliation: §Fuel Cell System Development Center, Toyota Motor Corporation, Mishuku, Susono, Shizuoka 410-1193, Japan.
authors.forename: Nobuaki
authors.initials: N
authors.lastname: Nonoyama
authors.affiliation: †Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
authors.forename: Kazunari
authors.initials: K
authors.lastname: Nakajima
authors.affiliation: †Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nishibayashi
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D008958:Models, Molecular; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D012997:Solvents; D013438:Sulfhydryl Compounds; D014867:Water; D012428:Ruthenium; D006859:Hydrogen; D007501:Iron; D000432:Methanol