Visible light-induced selective oxidation of cyclohexane to cyclohexanone on Cr-Si binary oxide with molecular oxygen

Cr-Si binary oxide prepared by a sol-gel method, when activated by visible light, catalyses highly selective oxidation of cyclohexane to cyclohexanone with molecular oxygen.     

Cobalt-catalyzed partial oxidation of olefins and ethers using molecular oxygen

Co(acac)₃ catalyzes the aerobic oxidation of vinyl aromatic compounds ArCH=CH₂ with formation of ArCO₂H and ArCHO, and also the aerobic oxidation of cyclic ethers with formation of the corresponding lactones.     

Visible-light-sensitive photocatalytic reaction on chromium-containing mesoporous silica: selective partial oxidation of propane with molecular oxygen

The photocatalytic reactivities of chromium-containing mesoporous silica molecular sieves (Cr-HMS) under visible light irradiation have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O groups. In the presence of propane with molecular oxygen, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein, with high selectivity, while a complete oxidation proceeded under UV light irradiation mainly to produce CO₂. The charge-transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactions.     

Acetonitrile-assisted highly selective photocatalytic epoxidation of olefins on Ti-containing silica with molecular oxygen

Highly selective photocatalytic epoxidation of olefins proceeds on Ti-containing silica with tetrahedrally coordinated Ti-oxide species with molecular oxygen and a simple addition of MeCN.     

Visible light-induced photoepoxidation of propene by molecular oxygen over chromia-silica catalysts

Highly dispersed chromate species on silica catalyse the selective epoxidation of propene to propene oxide (PO) by molecular oxygen under visible light irradiation with the same quantum yield as that under UV light irradiation.     

Visible light-induced 4-phenylthioxanthone-catalyzed aerobic oxidation of triarylphosphines

We report herein a visible light-induced oxidation of triarylphosphines under aerobic condition with excellent functional group tolerance. In this transformation, the photo catalyst 4-phenylthioxanthone acted as a photosensitizer for the in situ generation of singlet oxygen. This new approach provided a cheaper and greener method for the preparation of phosphine oxide, showing great advantages in environmental protocols.     

Visible light-induced hydroxyalkylation of 2H-benzothiazoles with alcohols via selectfluor oxidation

A visible-light induced metal-free approach was described for the hydroxyalkylation of 2H-benzothiazoles with alcohols by using selectfluor as the oxidant. A variety of 2H-benzothiazoles and alcohols could be tolerated, providing a mild and simple method for the synthesis of C2-hydroxyalkylated 2H-benzothiazoles in moderate to good yields. Besides, ethers were also compatible in this reaction, leading to corresponding C2 ether-substituted 2H-benzothiazoles with high regioselectivity.     

Highly efficient and metal-free oxidation of olefins by molecular oxygen under mild conditions

Highly efficient and metal-free aerobic oxidations of cyclohexene and styrene were successfully performed under mild conditions in the presence of 1,4-diamino-2,3-dichloro-anthraquinone and N-hydroxyphthalimide. When cyclohexene was oxidized, an 89% conversion and 71% selectivity for 2-cyclohexen-1-one was obtained under 0.3 MPa at 80 °C for 5 h. In the oxidation of styrene, a 77% conversion and 69% selectivity for benzaldehyde was obtained for 10 h. Furthermore, more olefins were efficiently oxidized to corresponding oxygenated products under mild conditions. All kinds of factors that affected cyclohexene oxidation were well investigated, and the possible reaction mechanism was provided.     

Visible light-induced hydroxyalkylation of 2H-benzothiazoles with alcohols via selectfluor oxidation

A visible-light induced metal-free approach was described for the hydroxyalkylation of 2H-benzothiazoles with alcohols by using selectfluor as the oxidant. A variety of 2H-benzothiazoles and alcohols could be tolerated, providing a mild and simple method for the synthesis of C2-hydroxyalkylated 2H-benzothiazoles in moderate to good yields. Besides, ethers were also compatible in this reaction, leading to corresponding C2 ether-substituted 2H-benzothiazoles with high regioselectivity.     

Photocatalytic oxidation of propylene with molecular oxygen over highly dispersed titanium, vanadium, and chromium oxides on silica

Photocatalytic oxidation of propylene with molecular oxygen at room temperature was investigated over various silica-supported metal oxides with low loading. The photocatalytic active site is assumed to be the isolated tetrahedrally coordinated metal oxides in the ligand-to-metal charge-transferred state, such as (Mdelta- -OLdelta+). Photocatalytic epoxidation of propylene into propylene oxide was promoted over silica-supported V and Ti oxides at steady state. Over silica-supported Cr oxide, the propylene oxide formation rate was remarkably decreased with the time course in the reaction. The oxidation state and the coordination environment of the supported Ti, V, and Cr oxide species were determined by diffuse reflectance UV-vis spectroscopy (DRS) and electron spin resonance (ESR). During the photocatalytic oxidation, the oxidation state of the Ti4+ species was not varied. On the other hand, the V5+ species was partially reduced to V4+ and the Cr6+ species was successively reduced to Cr5+ and Cr3+. An isotopic tracer study of the C3H6-18O2 reaction suggests the difference of the active oxygen species between TiO2/SiO2 and V2O5/SiO2. The active oxygen species on TiO2/SiO2 is derived from molecular oxygen. On the other hand, the photogenerated products on V2O5/SiO2 incorporate the lattice oxygen of the surface metal oxide species. It is suggested that the kinds of terminal ligand (hydroxyl or oxo) of the tetrahedrally coordinated metal oxides on silica decide the active oxygen species in the photocatalytic oxidation. A photoinduced hole center on the monohydroxyl (SiO)3Ti-OH species activates molecular oxygen that reacts with propylene. In the case of the monooxo (SiO)3V=O and dioxo (SiO)2Cr=O2 species, the photoactivated lattice oxygen (OL-) directly reacts with propylene.     

Liquid-phase oxidation of bromovinyl compounds with molecular oxygen

Liquid-phase oxidation of bromovinyl compounds with the aim to obtain the corresponding α-bromo acids was studied. Original Russian Text R.B. Bayatyan, B.E. Bayatyan, L.A. Saakyan, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 11, pp. 1870–1873.     

Efficient heterogeneous oxidation of alkylarenes with molecular oxygen

[reaction: see text] Ru(OH)x/Al2O3 efficiently catalyzes the heterogeneous aerobic oxygenation or oxidative dehydrogenation of alkylarenes to give the corresponding oxygenated or dehydrogenated products. Catalyst/product separation is very easy, and the recovered catalyst is reusable with retention of the high catalytic performance.     

Visible light-induced photocatalysts with reductive energy storage abilities

Reductive energy from visible light-responsive Au–TiO₂ photocatalyst, which is based on plasmon resonance absorption of Au nanoparticles, can be stored in WO₃ as a reductive energy storage material. About 60% of the charge stored in WO₃ is consumed on the WO₃ and the other 40% is on the Au–TiO₂ by reduction of ambient O₂. Electrochemically pretreated MoO₃ can also be used as an energy storage material.     

Visible light-induced electron transfer from di-mu-oxo-bridged dinuclear Mn complexes to Cr centers in silica nanopores

The compound (bpy) 2Mn (III)(mu-O) 2Mn (IV)(bpy) 2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single Cr (VI) charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of Mn (III)(mu-O) 2Mn (IV) demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of Cr (VI) centers. The FT-Raman spectrum upon visible light excitation of the Cr (VI)-O (II) --> Cr (V)-O (I) ligand-to-metal charge transfer reveals electron transfer from Mn (III)(mu-O) 2Mn (IV) (Mn-O stretch at 700 cm (-1)) to Cr (VI), resulting in the formation of Cr (V) and Mn (IV)(mu-O) 2Mn (IV) (Mn-O stretch at 645 cm (-1)). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments are corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (Delta E o = -0.6 V) remain after several minutes, which points to spatial separation of Cr (V) and Mn (IV)(mu-O) 2Mn (IV) as a consequence of hole (O (I)) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well-defined transition metal molecular units, with the ultimate goal of performing endothermic, multielectron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.     

Visible light-induced water oxidation on mesoscopic alpha-Fe2O3 films made by ultrasonic spray pyrolysis

Alpha-Fe(2)O(3) films having a mesoscopic leaflet type structure were produced for the first time by ultrasonic spray pyrolysis (USP) to explore their potential as oxygen-evolving photoanodes. The target of these studies is to use translucent hematite films deposited on conducting fluorine doped tin oxide (FTO) glass as top electrodes in a tandem cell that accomplishes the cleavage of water into hydrogen and oxygen by sunlight. The properties of layers made by USP were compared to those deposited by conventional spray pyrolysis (SP). Although both types of films show similar XRD and UV-visible and Raman spectra, they differ greatly in their morphology. The mesoscopic alpha-Fe(2)O(3) layers produced by USP consist mainly of 100 nm-sized platelets with a thickness of 5-10 nm. These nanosheets are oriented mainly perpendicularly to the FTO support, their flat surface exposing (001) facets. The mesoscopic leaflet structure has the advantage that it allows for efficient harvesting of visible light, while offering at the same time the very short distance required for the photogenerated holes to reach the electrolyte interface before recombining with conduction band electrons. This allows for water oxidation by the valence band holes even though their diffusion length is only a few nanometers. Distances are longer in the particles produced by SP favoring recombination of photoinduced charge carriers. Open-circuit photovoltage measurements indicate a lower surface state density for the nanoplatelets as compared to the round particles. These factors explain the much higher photoactivity of the USP compared to the SP deposited alpha-Fe(2)O(3) layers. Addition of hydrogen peroxide to the alkaline electrolyte further improves the photocurrent-voltage characteristics of films generated by USP indicating the hole transfer from the valence band of the semiconductor oxide to the adsorbed water to be the rate-limiting kinetic step in the oxygen generation reaction.     

Enzymatic-like mediated olefins epoxidation by molecular oxygen under mild conditions

Highly efficient epoxidation of olefins by molecular oxygen with catalytic amount of manganese meso-tetraphenylporphyrin (Mn(TPP)) at the ppm level were reported. The catalyst conferred high activity and selectivity for the olefins epoxidation under ambient temperature and atmospheric pressure. The turnover number (TON) of the catalyst could reach up to 700 million, which is comparable to enzyme catalysis.     

Catalytic oxidation of fluorobenzene by molecular oxygen

Kinetic and thermal-desorption methods have been applied to the oxidation of fluorobenzene by molecular oxygen. The catalytic oxidation mechanism for fluorobenzene is similar to that for benzene. A suggestion is made on why there is no fluoromaleic anhydride in the oxidation products from fluorobenzene.Translated from, Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 1, pp. 116–119, January–February, 1989.     

Visible light-induced thiocyanation of gem-difluorinated phosphonium salts

gem-Difluorinated phosphonium salts were generated from nitrones by methylation and reaction with (triphenylphosphonio)difluoroacetate. The phosphonium salts were subjected to visible light-induced phosphonium–thiocyanate exchange in the presence of ammonium thiocyanate, copper thiocyanate, and an iridium photocatalyst. The sequence of the reactions was performed in one pot affording thiocyanates attached to the difluoromethylene fragment.