title: Oxygen Evolution Catalyzed by a Mononuclear Ruthenium Complex Bearing Pendant SO3(-) Groups.
abstract: Rational molecular design of catalytic systems capable of smooth O-O bond formation is critical to the development of efficient catalysts for water oxidation. A new ruthenium complex was developed, which bears pendant SO3(-) groups in the secondary coordination sphere: [Ru(terpy)(bpyms)(OH2)] (terpy=2,2':6',2''-terpyridine, bpyms=2,2'-bipyridine-5,5'-bis(methanesulfonate)). Water oxidation driven by a Ce(4+) oxidant is distinctly accelerated upon introduction of the pendant SO3(-) groups in comparisons to the parent catalyst, [Ru(terpy)(bpy)(OH2)](2+) (bpy=2,2'-bipyridine). Spectroscopic, electrochemical, and crystallographic investigations concluded that the pendant SO3(-) groups promote the formation of an O-O bond via the secondary coordination sphere on the catalyst, whereas the influence of the pendant SO3(-) groups on the electronic structure of the [Ru(terpy)(bpy)(OH2)](2+) core is negligible. The results of this work indicate that modification of the secondary coordination sphere is a valuable strategy for the design of water oxidation catalysts.
authors.affiliation: Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787 (Japan).|Department of Chemistry, Faculty of Science, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan).|Current address: Department of Chemistry, Faculty of Science, Hokkaido University, North-10 West-8, Kita-ku, Sapporo 060-0810 (Japan).
authors.forename: Masaki
authors.initials: M
authors.lastname: Yoshida
authors.affiliation: Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787 (Japan).|ACT-C, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan).
authors.forename: Mio
authors.initials: M
authors.lastname: Kondo
authors.affiliation: Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787 (Japan).
authors.forename: Sena
authors.initials: S
authors.lastname: Torii
authors.affiliation: Department of Chemistry, Faculty of Science, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan).|International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, and Center for Molecular Systems (CMS), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan).
authors.forename: Ken
authors.initials: K
authors.lastname: Sakai
authors.affiliation: Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787 (Japan). masaoka@ims.ac.jp.
authors.forename: Shigeyuki
authors.initials: S
authors.lastname: Masaoka
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D002066:Busulfan / Q000031:analogs & derivatives; D002384:Catalysis; D002563:Cerium / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013461:Sulfur Oxides / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: C517923:(2,2'-6',2'')-terpyridine; D009942:Organometallic Compounds; D011725:Pyridines; D013461:Sulfur Oxides; D014867:Water; D002563:Cerium; D015082:2,2'-Dipyridyl; D012428:Ruthenium; D002066:Busulfan; C011118:sulfur trioxide; D010100:Oxygen
keywords: cerium; cooperative effects; homogeneous catalysis; ruthenium; water oxidation