title: How is the water molecule activated on metalloporphyrins? Oxygenation of substrates induced through one-photon/two-electron conversion in artificial photosynthesis by visible light.
abstract: The reaction mechanism of the highly efficient (phi = 0.60), selective photochemical epoxidation of alkenes sensitized by CO-coordinated tetra(2,4,6-trimethyl)phenylporphyrinatoruthenium(II) (Ru(II)TMP(CO)), with water acting both as an electron and oxygen atom donor, was investigated. The steady-state light irradiation of the reaction mixture indicated the formation of the Ru(II)TMP (CO) cation radical under neutral conditions, which was effectively trapped by an hydroxide ion to regenerate the starting sensitizer. By means of a laser flash photolysis experiment, the formation of the cation radical as the primary process from the triplet excited state of Ru(II)TMP(CO) was clearly observed. Four kinds of transients were detected in completely different ranges of the delay time: the excited triplet state of Ru(II)TMP(CO) [delay time region <20 micros], the cation radical of Ru(II)TMP(CO)(CH3CN) [20-50 micros], the hydroxyl-coordinated Intermediate [I] [50-200 micros], and the cyclohexane-attached Intermediate [II] [200 micros-8 ms]. A reaction mechanism was revealed that involves RuTMP(CO) cation radical formation from the triplet excited state of the sensitizer, followed by attack of an hydroxide ion to form an hydroxyl-coordinated Ru-porphyrin (Intermediate [I]) and subsequent reaction with cyclohexene to form Intermediate [II]. The kinetics for each step of the successive processes was carefully analyzed and their rate constants were determined. The two-electron oxidation of water by one-photon irradiation, as revealed in the photochemical epoxidation, is proposed to be one of the more promising candidates to get through the bottleneck of water oxidation in artificial photosynthesis.
authors.affiliation: Department of Applied Chemistry, Graduate Course of Engineering, Tokyo Metropolitan University, SORST, Japan Science and Technology, 1-1 Minami-Ohsawa, Hachiohji, Tokyo, 192-0397, Japan.
authors.forename: Tetsuya
authors.initials: T
authors.lastname: Shimada
authors.forename: Akihiro
authors.initials: A
authors.lastname: Kumagai
authors.forename: Shigeaki
authors.initials: S
authors.lastname: Funyu
authors.forename: Shinsuke
authors.initials: S
authors.lastname: Takagi
authors.forename: Dai
authors.initials: D
authors.lastname: Masui
authors.forename: Yu
authors.initials: Y
authors.lastname: Nabetani
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Tachibana
authors.forename: Donald A
authors.initials: DA
authors.lastname: Tryk
authors.forename: Haruo
authors.initials: H
authors.lastname: Inoue
mesh_terms: D000475:Alkenes / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry / Q000378:metabolism; D002412:Cations; D056831:Coordination Complexes / Q000737:chemistry / Q000378:metabolism; D004583:Electrons; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008027:Light; D008665:Metalloporphyrins / Q000737:chemistry* / Q000378:metabolism; D010084:Oxidation-Reduction / Q000528:radiation effects; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D010777:Photochemistry; D017785:Photons; D010788:Photosynthesis; D012428:Ruthenium / Q000737:chemistry / Q000378:metabolism; D014867:Water / Q000737:chemistry* / Q000378:metabolism
chemical_list: D000475:Alkenes; D002412:Cations; D056831:Coordination Complexes; D008665:Metalloporphyrins; D014867:Water; D002248:Carbon Monoxide; D012428:Ruthenium; D010100:Oxygen