35856-82-7Relevant articles and documents
Photocatalytic oxygenation of anthracenes and olefins with dioxygen via selective radical coupling using 9-mesityl-10-methylacridinium ion as an effective electron-transfer photocatalyst
Kotani, Hiroaki,Ohkubo, Kei,Fukuzumi, Shunichi
, p. 15999 - 16006 (2004)
Visible light irradiation of the absorption band of 9-mesityl-10- methylacridinium ion (Acr+-Mes) in an O2-saturated acetonitrile (MeCN) solution containing 9,10-dimethylanthracene results in formation of oxygenation product, i.e., dimethylepidioxyanthracene (Me 2An-O2). Anthracene and 9-methylanthracene also undergo photocatalytic oxygenation with Acr+-Mes to afford the corresponding epidioxyanthracenes under the photoirradiation. In the case of anthracene, the further photoirradiation results in formation of anthraquinone as the final six-electron oxidation product, via 10-hydroxyanthrone, accompanied by generation of H2O2. When anthracene is replaced by olefins (tetraphenylethylene and tetramethylethylene), the photocatalytic oxygenation of olefins affords the corresponding dioxetane, in which the O-O bond is cleaved to yield the corresponding ketones. The photocatalytic oxygenation of anthracenes and olefins is initiated by photoexcitation of Acr+-Mes, which results in formation of the electron-transfer state: Acr?- Mes?+, followed by electron transfer from anthracenes and olefins to the Mes?+ moiety together with electron transfer from the Acr? moiety to O2. The resulting anthracene and olefin radical cations undergo the radical coupling reactions with O 2?- to produce the epidioxyanthracene (An-O 2) and dioxetane, respectively.
Dihydrogen trioxide (HOOOH) photoelimination from a platinum(IV) hydroperoxo-hydroxo complex
Wickramasinghe, Lasantha A.,Sharp, Paul R.
supporting information, p. 13979 - 13982 (2015/01/08)
Photolysis (380 nm) of trans-Pt(PEt3)2(Cl)(OH)(OOH)(4-trifluoromethylphenyl) (1) at -78 °C in acetone-d6 or toluene-d8 yields HOOOH (16-20%) and trans-Pt(PEt3)2(Cl)(4-trifluoromethylphenyl) (2). Also observed in acetone-d6 are H2O2, (CD3)2C(OH)(OOH), and (CD3)2C(OOH)2. Thermal decomposition or room-temperature photolysis of 1 gives O2, water, and 2. Computational modeling (DFT) suggests two intramolecular hydrogen-bonding-dependent triplet pathways for the photolysis and two possible pathways for the thermolysis, one involving proton transfer from the OOH to the OH ligand and the other homolysis of the Pt-OOH bond, abstraction of the OH ligand, and decomposition of the resulting H2O3. Trapping studies suggest the latter pathway.
