3112-88-7Relevant articles and documents
Molybdenum (VI)-functionalized UiO-66 provides an efficient heterogeneous nanocatalyst in oxidation reactions
Afzali, Niloufar,Kardanpour, Reihaneh,Zadehahmadi, Farnaz,Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Mechler, Adam,Mohammadpoor-Baltork, Iraj,Bahadori, Mehrnaz
, (2019)
A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr6 nodes in the structure of the well-known UiO-66 metal–organic framework (MOF). The structure of the UiO-66 before and after Mo (VI) immobilization was confirmed with XRD, DR-FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H2O2 in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material.
New oxovanadium and dioxomolybdenum complexes as catalysts for sulfoxidation: experimental and theoretical investigations of E and Z isomers of ONO tridentate Schiff base ligand
Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Moghimi, Atefeh,Munawar, Khurram Shahzad,Rudbari, Hadi Amiri
, (2021/06/23)
A new ONO-tridentate Schiff base ligand (H2L) derived by the condensation of nicotinic hydrazide with 5-chlorosalicylaldehyde has been prepared and characterized by combustion analysis (CHN), FT-IR and multinuclear (1H and 13C) NMR spectroscopy. The crystalline nature and molecular structure of the ligand were confirmed by single-crystal X-ray diffraction analysis. Furthermore, the optimized structural parameters of the four possible configurations of the ligand including Z and E stereoisomers each containing two tautomeric forms (enol and keto) have also been investigated. The theoretical parameters were calculated by performing the DFT method using the B3LYP/Def2-TZVP level of theory. In addition to this, dioxomolybdenum(VI) (MoO2L) and oxovanadium(V) (VOL) complexes with the entitled Schiff base ligand have also been prepared and characterized by different techniques. Then, the catalytic efficiencies of synthesized VOL and MoO2L complexes were also explored for the oxidation of sulfides using 30% aqueous H2O2 as a source of oxygen. These homogeneous catalysts showed excellent catalytic activities in the oxidation of both aromatic and aliphatic sulfides.
Ceramic boron carbonitrides for unlocking organic halides with visible light
Yuan, Tao,Zheng, Meifang,Antonietti, Markus,Wang, Xinchen
, p. 6323 - 6332 (2021/05/19)
Photochemistry provides a sustainable pathway for organic transformations by inducing radical intermediates from substrates through electron transfer process. However, progress is limited by heterogeneous photocatalysts that are required to be efficient, stable, and inexpensive for long-term operation with easy recyclability and product separation. Here, we report that boron carbonitride (BCN) ceramics are such a system and can reduce organic halides, including (het)aryl and alkyl halides, with visible light irradiation. Cross-coupling of halides to afford new C-H, C-C, and C-S bonds can proceed at ambient reaction conditions. Hydrogen, (het)aryl, and sulfonyl groups were introduced into the arenes and heteroarenes at the designed positions by means of mesolytic C-X (carbon-halogen) bond cleavage in the absence of any metal-based catalysts or ligands. BCN can be used not only for half reactions, like reduction reactions with a sacrificial agent, but also redox reactions through oxidative and reductive interfacial electron transfer. The BCN photocatalyst shows tolerance to different substituents and conserved activity after five recycles. The apparent metal-free system opens new opportunities for a wide range of organic catalysts using light energy and sustainable materials, which are metal-free, inexpensive and stable. This journal is
On the important transition of sugar-based surfactant as a microreactor for C-S coupling in water: From micelle to vesicle
Ge, Xin,Lei, Qiuyun,Liao, Xiong,Liu, Xuemin,Song, Weili,Wu, Lei,Wu, Siyuan,Zhou, Shaodong
, (2021/09/15)
A reversible, temperature-induced micelle-to-vesicle transition of a sugar-based pseudogemini surfactant (C11D12) was employed for copper-catalyzed C-S coupling in water. The phase behavior and morphology of the C11D12 aqueous solution were investigated by DLS and cryo-TEM. The aggregates undergo a series of transitions upon increasing the temperature: spherical micelles were initially transformed into large vesicles, but they eventually transformed into smaller vesicles. The vesicular catalytic protocol accommodates an excellent substrate scope with moderate to high yields. The mechanisms of temperature-induced aggregate transition and vesicular catalysis were elucidated by experimental results and DFT calculations. It was revealed that the charge layer of the vesicle grants stronger nucleophilicity to the PhSO2-Cu-D12Ga intermediate. Furthermore, the aqueous reaction medium can be recycled and reused several times after easily separating the precipitated product.
Synthesis, spectral characterization, SC-XRD, HSA, DFT and catalytic activity of novel dioxovanadium(V) complex with aminobenzohydrazone Schiff base ligand: An experimental and theoretical approach
Ashfaq, Muhammad,Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Munawar, Khurram Shahzad,Tahir, Muhammad Nawaz
, (2021/07/28)
A new dioxovanadium(V) complex was prepared by the reaction of VO(acac)2 with a tridentate ONO donor Schiff base, derived by condensing 3-ethoxysalicylaldehyde and 4-aminobenzohydrazide. The structures of synthesized products were characterized spectroscopically through FT-IR, 1H & 13C NMR and by elemental composition through combustion analysis. The structure of the complex was determined with the help of single crystal X-ray crystallography. It was inferred from the diffraction data that the geometry around the central metal ion in the complex is distorted square pyramidal. The tridentate Schiff base ligand is bonded to the central metal through the oxygen of the carbonyl group, the deprotonated phenolic oxygen atom and the azomethine nitrogen. The pyramid base is completed by other oxo ligands that are in cis positions. The theoretical calculations, performed by DFT using B3LYP/Def2-TZVP level of theory, determined that the intended outcomes are in compliance with the actual consequences. Furthermore, the catalytic potential of the vanadium complex was explored for the selective oxidation of the aryl and alkyl sulfides to the corresponding sulfones in the presence of 30% aqueous H2O2 in ethanol. In this work, rPBE and B3LYP methods are used to locate transition structures and to compare free energies of reactants, transition structures and the products involved in the reaction. Analyzing nudge elastic band data shows that the barrier free energy for the oxidation of sulfide to sulfoxide and sulfone are 13 and 83 kcal.mol?1, respectively. The main advantages of the present catalytic study are high yields of the products, less time required for the completion of the reaction and simple work-out procedure.
Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
supporting information, p. 8691 - 8695 (2021/10/22)
A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
Synthesis, spectra (FT-IR, NMR) investigations, DFT, FMO, MEP, NBO analysis and catalytic activity of MoO2(VI) complex with ONO tridentate hydrazone Schiff base ligand
Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Munawar, Khurram Shahzad
, (2021/08/16)
A new dioxomolybdenum(VI) complex has been successfully prepared by the reaction of an ONO donor Schiff base, derived by condensing 4-amino-2-hydroxybenzohydrazide and 3-ethoxysalicylaldehyde, with MoO2(acac)2. The structures of synthesized products were explored spectroscopically through FT-IR, 1H & 13C NMR and by elemental composition (CHN) through combustion analysis. The tridentate Schiff base ligand is bonded to the central metal through its deprotonated enolic and phenolic oxygen atoms and by the nitrogen of the azomethine group. The interpretation of the data obtained through diffraction analysis validates the distorted octahedral geometry for the prepared metal complex. Furthermore, the catalytic potential of the molybdenum complex was explored for the selective oxidation of the aryl and alkyl sulfides to the corresponding sulfones in the presence of 30% aqueous H2O2 in ethanol. The main edge of the present catalytic work is the accomplishment of reaction in a short period of time, high percentage yield and easy work-up procedure.
Highly efficient and selective aqueous aerobic oxidation of sulfides to sulfoxides or sulfones catalyzed by tungstate-functionalized nanomaterial
Luque, Rafael,Rajabi, Fatemeh,Vessally, Esmail,Voskressensky, Leonid
, (2021/10/08)
A Br?nsted acidic ionic solid comrising tungstate-functionaized polyorganosiloxane framework (PMO-IL-WO42?) efficiently catalysed aerobic oxidation of sulfides in aqueous medium. The catalyst can selectively produce sulfoxides or sulfones by running the reaction at room temperature or 50 °C, respectively. Because of the ionic liquid-based charged surface containing hydrophobic organic functional groups and hydrophilic sulfonic acid group, the synergestic hydrophobic/hydrophilic and redox effect of PMO-IL-WO42- as water-friendly interfacial nanocatalyst simplifies and enhances the activity and selectivity toward the target sulfoxides or sulfones in water. Moreover, the PMO-IL-WO42- nanocatalyst exhibited outstanding stability and activity and can be recycled eight reaction runs without any significant activity and selectivity loss.
COMPOSITES, METHODS AND USES THEREOF
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Page/Page column 26, (2021/06/04)
The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
Synthesis of sulfone derivatives via palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides
Luo, Jin,Wan, Juelin,Wang, Tao,Yu, Weijie
supporting information, (2021/12/31)
A palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides for the synthesis of various benzyl sulfones is reported. This novel protocol shows widespread functional group tolerance, leading to the desired sulfones in moderate to excellent yields.
