Search results for "Reti"
showing 10 items of 16256 documents
Hierarchical Beta zeolites obtained in concentrated reaction mixtures as catalysts in tetrahydropyranylation of alcohols
2020
Abstract Hierarchical zeolites consisting of Beta nanoparticles (15–40 nm) were obtained via hydrothermal treatment of a concentrated zeolite gel-precursor (H2O/Si = 2.5–14) without utilization of complex SDAs. The proposed approach is based on the formation of a large number of zeolite nuclei under particular crystallization conditions, followed by their agglomeration resulting in the dense packing of the particles preventing their further growth. The micelles of cetyltrimethylammonium bromide (CTAB) can be used to additionally limit the growth of zeolite nanoparticles during hydrothermal treatment of concentrated reaction mixtures. Such deceleration of crystallization promotes the formati…
Kinetic and Electrochemical Studies of the Oxidative Addition of Demanding Organic Halides to Pd(0): the Efficiency of Polyphosphane Ligands in Low P…
2013
International audience; Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C–C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C–C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp2C–H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph…
Enantiomeric Resolution of Asymmetric-Carbon-Free Binuclear Double-Stranded Cobalt(III) Helicates and Their Application as Catalysts in Asymmetric Re…
2018
A series of double-stranded binuclear helicates [Co2(H1)2]4+, [Co2(H2)2]4+, and [Co2(H3)2]4+, derived from monodeprotonated bis-pyridyl hydrazine-based ligands of H21, H22, and H23 with one, two, and three -CH2 spacers, were obtained. These asymmetric-carbon-free racemic helicates were separated into their ΔΔ and ΛΛ enantiomers. The resolved helicates were examined for the first time as enantioselective catalysts in asymmetric benzoylation and nitroaldol reactions.
Viewpoint: Atomic-Scale Design Protocols toward Energy, Electronic, Catalysis, and Sensing Applications
2019
Nanostructured materials are essential building blocks for the fabrication of new devices for energy harvesting/storage, sensing, catalysis, magnetic, and optoelectronic applications. However, because of the increase of technological needs, it is essential to identify new functional materials and improve the properties of existing ones. The objective of this Viewpoint is to examine the state of the art of atomic-scale simulative and experimental protocols aimed to the design of novel functional nanostructured materials, and to present new perspectives in the relative fields. This is the result of the debates of Symposium I "Atomic-scale design protocols towards energy, electronic, catalysis…
Total Synthesis of (-)-Oxycodone via Anodic Aryl-Aryl Coupling.
2019
A fully regio- and diastereoselective electrochemical 4a–2′-coupling of a 3′,4′,5′-trioxygenated laudanosine derivative enables the synthesis of the corresponding morphinandienone. This key intermediate is further transformed into (−)-oxycodone through conjugate nucleophilic substitution for E-ring closure and [4 + 2] cycloaddition with photogenerated singlet oxygen to accomplish diastereoselective hydroxylation at C-14. The anodic transformation provides high yields and can be performed under constant current conditions both in a simple undivided cell or in continuous flow.
Effect of Iodination on the Photophysics of the Laser Borane anti-B18H22: Generation of Efficient Photosensitizers of Oxygen
2019
Treatment of the laser borane anti-B18H22 (compound 1) with iodine in ethanol gives the monoiodinated derivative 7-I-anti-B18H21 (compound 2) in 67% yield, or, by reaction with iodine or ICl in the presence of AlCl3 in dichloromethane, the diiodinated derivative 4,4'-I2-anti-B18H20 (compound 3) in 85% yield. On excitation with 360 nm light, both compounds 2 and 3 give strong green phosphorescent emissions (λmax = 525 nm, ΦL = 0.41 and λmax = 545 nm, ΦL = 0.71 respectively) that are quenched by dioxygen to produce O2(1Δg) singlet oxygen with quantum yields of ΦΔ = 0.52 and 0.36 respectively. Similarly strong emissions can be stimulated via the nonlinear process of two-photon absorption when …
Photo-Chromium: Sensitizer for Visible-Light-Induced Oxidative C−H Bond Functionalization-Electron or Energy Transfer?
2017
The chromium(III) sensitizer [Cr(ddpd)2]3+ - based on an earth-abundant metal center - possesses a unique excited state potential energy landscape (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). The very large energy gap between the redox active and substitutionally labile 4T2 state and the long-lived low-energy 2E spin-flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron transfer pathways from the ultrashort-lived excited 4T2 state. This specific excited state reactivity enables a …
Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands
2020
The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt–Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalated platinum(II) complexes (Pt–Ar) are essentially associated with the platinum-cyclometalated unit. Room-temperature emission of the Pt–Ar complexes was attributed to phosphorescence in agreement with DFT calculations. Broad nanosecond (ns)-transient absorption spectra were observed with decays approximately identical to those obtained from the emi…
Three Co(II) Metal-Organic Frameworks with Diverse Architectures for Selective Gas Sorption and Magnetic Studies.
2019
Three Co(II) metal–organic frameworks, namely, {[Co2(L)2(OBA)2(H2O)4]·xG}n (1), {[Co(L)0.5(OBA)]·xG}n (2), and {[Co2(L)2(OBA)2(H2O)]·DMA·xG}n (3) [where L = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene, H2OBA = 4,4′-oxybisbenzoic acid, DMF = dimethylformamide, DMA = dimethylacetamide, and G denotes disordered guest molecules], have been synthesized under diverse reaction conditions through self-assembly of a bent dicarboxylate and a linear spacer with a Co(II) ion. While 1 is crystallized at room temperature in DMF to form a 2D layer structure, 2 is formed by the assembly of similar components under solvothermal conditions with a 3D network structure. On the other hand, changing the solvent t…
Magnetostructural correlations in CuII−NC−WV linkage: the case of [CuII(diimine)]2+−[WV(CN)8]3− 0D assemblies
2009
International audience; We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [CuII(phen)3]2{[CuII(phen)2]2[WV(CN)8]2}(ClO4)2·10H2O (phen = 1,10-phenanthroline) (1) and {[CuII(bpy)2]2[WV(CN)8]} {[CuII(bpy)2][WV(CN)8]}·4H2O (bpy = 2,2′-bipyridyl) (2). Compound 1 consists of cyano-bridged [CuII2WV2]2− molecular rectangles and isolated [CuII(phen)3]2+ complexes. The molecular structure of 2 reveals cyano-bridged trinuclear [CuII2WV]+ and dinuclear [CuIIWV]− ions. Magnetic interactions in 1 are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic CuII−NC−WV units (J1 = +39(4) cm−1) interacting ant…