Highly efficient and selective epoxidation of alkenes by photochemical oxygenation sensitized by a ruthenium(II) porphyrin with water as both electron and oxygen donor.
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.
Department of Applied Chemistry, Graduate Course of Engineering, Tokyo Metropolitan University, and CREST, Japan Science and Technology, Hachiohji, Tokyo, Japan.
Shigeaki
S
Funyu
Takehiko
T
Isobe
Shinsuke
S
Takagi
Donald A
DA
Tryk
Haruo
H
Inoue
D000475:Alkenes / Q000737:chemistry*; D040761:Biomimetic Materials / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D006863:Hydrogen-Ion Concentration; D008027:Light; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010103:Oxygen Isotopes; D010777:Photochemistry; D011166:Porphyrins / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D000475:Alkenes; D004852:Epoxy Compounds; D009942:Organometallic Compounds; D010103:Oxygen Isotopes; D011166:Porphyrins; D014867:Water; D012428:Ruthenium; D010100:Oxygen