Visible light irradiation of a reaction mixture of carbonyl-coordinated tetra(2,4,6-trimethyl)phenylporphyrinatoruthenium(II) (Ru(II)TMP(CO)) as a photosensitizer, hexachloroplatinate(IV) as an electron acceptor, and an alkene in alkaline aqueous acetonitrile induces selective epoxidation of the alkene with high quantum yield (Phi = 0.6, selectivity = 94.4% for cyclohexene and Phi = 0.4, selectivity = 99.7% for norbornene) under degassed conditions. The oxygen atom of the epoxide was confirmed to come from a water molecule by an experiment with H(2)(18)O. cis-Stilbene was converted into its epoxide, cis-stilbeneoxide, without forming trans-stilbeneoxide. trans-Stilbene, however, did not exhibit any reactivity. Under neutral conditions, an efficient buildup of the cation radical of Ru(II)TMP(CO) was observed at the early stage of the photoreaction, while an addition of hydroxide ion caused a rapid reaction with the cation radical to promote the reaction with reversion to the starting Ru(II)TMP(CO). A possible involvement of a higher oxidized state of Ru such as Ru(IV), Ru(V), Ru(VI) through a dismutation of the Ru(III) species was excluded by an experiment with Ru(VI)TMP(O)(2). Decarbonylation of the Ru complex was also proven to be invalid. A reaction mechanism involving an electron transfer from the excited triplet state of Ru(II)TMP(CO) to hexachloroplatinate(IV) and subsequent formation of OH(-)-coordinated Ru(III) species, leading to an oxo-ruthenium complex as the key intermediate of the photochemical epoxidation, was postulated.

Recent progress in the field of artificial photosynthesis is reviewed. Among various approaches to oxidizing the water molecule, attention has been focused on the two-electron chemical conversion processes mediated by metallo-porphyrins upon visible light irradiation. Photochemical oxygenation reactions such as the epoxidation of alkenes sensitized by ruthenium(II) porphyrins with water as both electron and oxygen atom donor have been found. Ru porphyrin induces highly efficient two-electron oxidation of water with a quantum yield of 60 % to form an epoxide from the alkene with high selectivity. The water molecule serves as both an efficient electron and oxygen atom donor in the reaction, in which the oxygen atom of water is incorporated in a useful product, i.e., epoxide.

Iridium(III) luminophores as energy donors for sensitised emission from lanthanides in the visible and near-infrared regions, N. M. Tart et al.,

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.