- Kinetic studies on the oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane; Absolute rate constants and activation parameters for 4-nitrophenyl methyl sulfide and sulfoxide
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The oxidations of methyl 4-nitrophenyl sulfide and sulfoxide by dimethyldioxirane, in acetone and mixtures of acetone with water, methanol, acetonitrile and hexane, have been followed by UV-Vis spectroscopy to monitor the decay of the substrates. The data show that, under all the conditions studied, both oxidations obey second-order kinetics. Grunwald-Winstein and Kamlet-Taft analyses of the influence of solvents on the second-order rate constants have been used to obtain mechanistic information on the two reactions. Activation parameters for the two oxidations in acetone and aqueous acetone have been calculated from rate constants for reactions in the temperature range 283-313 K and compared with those from sulfide and sulfoxide oxidations with other oxidants. For sulfoxide oxidations in acetone and 1-20% v/v water in acetone, the results support a concerted nucleophilic displacement by sulfur of oxygen from dimethyldioxirane with the rate being dependent on the solvent's polarity. Sulfide oxidations in acetone and 1-5% v/v water in acetone also proceed by a concerted mechanism. However, in the most polar solvent system studied, 20% v/v water in acetone, the mechanism changes in favour of a two-step reaction involving a betaine intermediate. Importantly, the sulfide oxidation shows a different solvent dependence to that of the sulfoxide, with the rate of oxidation being determined by the hydrogen bond donor capacity and electron-pair donicity of the solvent. This journal is The Royal Society of Chemistry.
- Hanson, Peter,Hendrickx, Ramon A. A. J.,Lindsay Smith, John R.
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- Alkylimidazolium/alkylpyridinium octamolybdates catalyzed oxidation of sulfides to sulfoxides/sulfones with hydrogen peroxide
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β-Mo8O26 based alkyl imidazolium and pyridinium salts of general formula [Bmim]4Mo8O26 (Bmim = 1-butyl-3-methylimidazolium), [Hmim]4Mo8O26 (Hmim = 1-hexyl-3-methylimidazolium), [Dhmim]4Mo8O26 (Dhmim = 1.2-dimethyl-3-hexylimidazolium) and [Hpy]4Mo8O26 (Hpy = 1-hexylpyridinium) have been used as catalysts for the oxidation of sulfides using 30% hydrogen peroxide as oxidant. The examined β-Mo8O26 salts prove to be highly active and are self-separating. A high selectivity towards either sulfoxides or sulfones can be nicely controlled by variation of the reaction conditions. In both cases, the catalysts can be recycled and reused for several times without significant loss of activity, representing a good stability of the catalysts.
- Ye, Jin-Xin,Wang, Jing-Yun,Wang, Xin,Zhou, Ming-Dong
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- Haloperoxidase activity of oxovanadium(V) thiobisphenolates
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By employing the 2,2′-thiobis(2,4-di-tert-butylphenolate) ligand (SL2-) a novel oxovanadium(V) complex, (PPh 4)2[SLV(O)(μ-O)2-O) 2V(O)SL] (1), was synthesised that exhibits haloperoxidase activity: on addition of H2O2 a sequence of successive peroxide formation and intramolecular thioether oxidation events (sulfoxide and sulfone) led to a mixture of five products, which were all identified unambiguously, partly through an independent synthesis and characterisation. It was shown that internal thioether oxidation proceeds through peroxide formation, but the sulfoxidation of external thioether functions requires further activation of the peroxide function by protons or alkyl cations. Consistently, the employment of tBuOOH instead of H2O2 led to a very active system for the catalytic sulfoxidation of thioethers.
- Werncke, C. Gunnar,Limberg, Christian,Knispel, Christina,Metzinger, Ramona,Braun, Beatrice
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- Molybdenum-doped α-MnO2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation
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Oxygenation of sulfides to sulfoxides and/or sulfones is an important transformation, and the development of efficient heterogeneous catalysts for oxygenation, which can utilize O2 as the terminal oxidant, is highly desired. In this study, we have successfully developed manganese oxide-based efficient heterogeneous catalysts for aerobic oxygenation of sulfides. Firstly, we prepared four kinds of manganese oxides possessing different crystal structures, such as α-MnO2, β-MnO2, γ-MnO2, and δ-MnO2, and their structure-activity relationships were examined for the aerobic oxygenation of thioanisole. Amongst them, α-MnO2 showed the best catalytic performance for the oxygenation. Moreover, α-MnO2 was highly stable during the catalytic oxygenation possibly due to the tunnel K+ ions. In order to further improve the catalytic performance of α-MnO2, substitutional doping of transition metal cations, such as Mo6+, V5+, Cr3+, and Cu2+, into the framework was carried out. Undoped α-MnO2 possessed a fibrous morphology. When high-valent transition metal cations were doped, especially Mo6+, the lengths of the fibers drastically shortened to form grain-like aggregates of ultrafine nanocrystals, resulting in an increase in specific surface areas and the numbers of catalytically active surface sites. In the presence of Mo6+-doped α-MnO2 (Mo-MnO2), various kinds of sulfides could efficiently be oxidized to the corresponding sulfoxides as the major products. The observed catalysis was truly heterogeneous, and Mo-MnO2 could repeatedly be reused while keeping its high catalytic performance. Besides sulfide oxygenation, Mo-MnO2 could efficiently catalyze several aerobic oxidative functional group transformations through single-electron transfer oxidation processes, namely, oxygenation of alkylarenes, oxidative α-cyanation of trialkylamines, and oxidative S-cyanation of benzenethiols.
- Uematsu, Tsubasa,Miyamoto, Yumi,Ogasawara, Yoshiyuki,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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- Oxidation of aryl methyl sulfoxides by oxo(salen)manganese(V) complexes and the reactivity-selectivity principle
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The oxidation of various para-substituted phenyl methyl sulfoxides with several substituted oxo(salen)manganese(V) complexes follows an overall second-order kinetics that is first-order in sulfoxide and in oxo(salen)manganese(V) complex. Electron-releasing substituents in sulfoxides and electron-withdrawing substituents in oxo(salen)manganese(V) complexes enhance the rate of oxidation. The less nucleophilic sulfoxides are more sensitive to substituent effect (p = -2.44) compared to the corresponding sulfides (p = -1.86). These results are interpreted with a common mechanism involving the electrophilic attack of the oxidant on the sulfur center of the substrate. Correlation analyses show the presence of an inverse relationship between reactivity and selectivity in the reactions of various sulfoxides with a given oxo(salen)manganese(V) complex and vice versa. Mathematical treatment of the results leads to the conclusion that this redox system falls under strong reactivity-selectivity principle.
- Chellamani, Arunachalam,Kulanthaipandi, Periasamy,Rajagopal, Seenivasan
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- A Novel and Efficient Method for Oxidizing Sulfides to Sulfones with the HOF*CH3CN System
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The HOF*CH3CN complex, made directly by passing fluorine through aqueous acetonitrile, oxidizes all types of sulfides to the corresponding sulfones and also offering a way to make 18O containing sulfone derivatives.
- Rozen, Shlomo,Bareket, Yifat
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- Discovery of a New Family of Polyoxometalate-Based Hybrids with Improved Catalytic Performances for Selective Sulfoxidation: The Synergy between Classic Heptamolybdate Anions and Complex Cations
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A series of functional cation-regulated isopolymolybdate-based organic-inorganic hybrid compounds, Na2H2[Mo4O12(C8H17O5N)2]·10H2O (1), Na2[M(Bis-tris)(H2O)]2[Mo7O24]·10H2O [M = Cu, 2; Ni, 3; Co, 4; Zn, 5; Bis-tris = 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol], and (NH4)2[M(Bis-tris)(H2O)]2[Mo7O24]·6H2O (M = Zn, 6; Cu, 7), were synthesized and characterized toward advanced molecular catalyst design. Compound 1 is a covalently bonded adduct, and its self-assembly process can be probed by electrospray ionization mass spectrometry (ESI-MS). Compounds 2-7 are polyoxometalate (POM)-based hybrids containing classic heptamolybdate anions and complex cations with Bis-tris ligands. All of these compounds showed remarkable catalytic effects for selective sulfide oxidation. To the best of our knowledge, compound 5 presents the best catalytic activity so far among the reported hybrid materials with common easily synthesized small-molecule POM clusters and also exhibits outstanding reliability. The conclusion of the catalytic effect is drawn from the results that Zn-based compounds have better catalytic effects than other transition-metal-containing compounds and the compound constructed by Na+ has higher catalytic activity than that constructed by NH4 +. The mechanism studies show that the improvements of the catalytic performance are caused by the synergy between classic heptamolybdate anions and complex cations. ESI-MS data and UV-vis spectra revealed that the POM anions can form intermediate peroxomolybdenum units during catalytic reaction. Further, the combination of the substrate thioanisole with complex cations was characterized by NMR experiments and UV-vis spectra. Thus, a new synergistic mechanism of anions and cations is proposed in which the activated thioanisole is used as a nucleophile to attack the peroxomolybdenum bonds, and this provides a new strategy in the design of reliable POM-based catalysts.
- Zhang, Yin,Yu, Wei-Dong,Li, Bin,Chen, Zheng-Fan,Yan, Jun
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- Chemistry of Oxaziridines. 7. Kinetics and Mechanism of the Oxidation of Sulfoxides and Alkenes by 2-Sulfonyloxaziridines. Relationship to the Oxygen-Transfer Reactions of Metal Peroxides
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A kinetic investigation of the oxidation of sulfoxides to sulfones and the epoxidation of 1-methylcyclohexene by a series of aryl-substituted 2-sulfonyloxaziridines, 5 and 9, are described.On the basis of linear free energy relationships and a qualitative frontier molecular orbital analysis, an SN2-type mechanism is proposed that involves displacement of a substituted sulfonylimine from the oxaziridine functional group by the lone pair on the sulfur or the ?-bond of the alkene.The reaction rates are subject to both steric and electronic effects with only a minor amount of negative charge residing on the leaving group.The relationship and similarity of oxygen-transfer mechanisms for 2-sulfonyloxaziridines, metal peroxides such as the Sharpless reagent, dioxiranes, and peracids is discussed.
- Davis, Franklin A.,Billmers, Joanne M.,Gosciniak, Donald J.,Towson, James C.,Bach, Robert D.
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- Fluorous biphasic catalytic oxidation of sulfides by molecular oxygen/2,2-dimethylpropanal
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The use of perfluoroalkyl-substituted cobalt complexes as catalysts for the oxidation of alkyl aryl sulfides with molecular oxygen/2,2-dimethypropanal has been studied in a fluorous organic biphasic system. The addition of very small amounts of a Co11-tetraarylporphyrin (Co-4) led to increased substrate conversions (67-100%). Sulfoxide was generally obtained as the main product, together with variable quantities of sulfone (0-100%), depending on the nature of the substrate. A perfluoroalkyl-substituted Co11-phthalocyanine (Co-6) proved to be less efficient with regard to substrate conversion (40-78%), but afforded sulfoxides selectively. Although the mechanism has not been investigated in detail, the reaction probably proceeds through a free-radical oxidative process, initiated by the Co11 complexes. The attempts at recycling the catalysts through phase separation were partly ineffectual owing to their instability under the reaction conditions, which is more pronounced in the case of Co-6.
- Colonna, Stefano,Gaggero, Nicoletta,Montanari, Fernando,Pozzi, Gianluca,Quici, Silvio
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- Electron transfer reactions of organic sulfoxides with photochemically generated ruthenium(III)-polypyridyl complexes
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The electron transfer (ET) reaction of aryl methyl sulfoxides with ruthenium(III)-polypyridine complexes is sensitive to the change of substituent in the aryl moiety of ArS(O)CH3 and ligand of Ru(III) complex. The detection of sulfoxide radical cation as the transient by conventional flash photolysis confirms ET in the rate-controlling step. The successful application of Marcus cross relation of ET leads to the evaluation of self-exchange rate constant of ArS+(O)CH3/ArS(O)CH3 as 4.0×105M-1s-1 similar to organic sulfides. Comparison with the reactivity of iron(III)-polypyridyl complexes points out that both reactivity and ρ values are higher with Ru(III) complexes.
- Ganesan, Muniyandi,Sivasubramanian, Veluchamy Kamaraj,Rajagopal, Seenivasan,Ramaraj, Ramasamy
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- Organosulfur oxidation by hydrogen peroxide using a dinuclear Mn-1,4,7-trimethyl-1,4,7-triazacyclononane complex
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A mechanistic study of organosulfide oxidation by H2O 2, using a dinuclear manganese complex as the catalyst, has revealed an unusual switch in the philicity of the oxidant for the first and the second oxygen transfer steps; this switch has been exploited to tune selectivity for each of the products.
- Smith, John R. Lindsay,Murray, Jane,Walton, Paul H.,Lowdon, Terry R.
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- A temperature-resolved assembly of a series of the largest scandium-containing polyoxotungstates
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We report a temperature-resolved assembly of a series of novel nanoscale hexameric Sc-containing polyoxometalates of {Sb6Sc11W60}, {Sb8Sc7W60}, and {Sb8Sc6W60}. These compounds include the largest Sc-containing polyoxotungstates and contain the largest number of Sc3+ ions of any polyoxotungstates reported to date.
- Cai, Zhen-Wen,Yang, Tao,Qi, Yan-Jie,Li, Xin-Xiong,Zheng, Shou-Tian
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- Electron transfer reactions of iron(III)-polypyridyl complexes with organic sulfoxides
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The redox reactions of four iron(III)-polypyridyl complexes with six aryl methyl sulfoxides have been investigated by spectrophotometric technique. The reaction follows clean second order kinetics and proceeds through rate determining electron transfer (ET) from organic sulfoxides to iron(III). The Marcus cross-reaction relation has been applied to obtain the self exchange rate constant for the ArSOR/ArS·+(O)R couple as 1.3×107M-1s-1. The application of Marcus theory to this ET reaction shows that the contribution of inner sphere reorganization energy is 0.4eV. The rate constant and reaction constant values observed with organic sulfoxides are small compared with organic sulfides towards the same oxidant Fe(NN)33+.
- Adaikalasamy, Kulandai John,Venkataramanan, Natarajan Sathiyamoorthy,Rajagopal, Seenivasan
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- Peroxotungstates immobilized on multilayer ionic liquid brushes-modified silica as an efficient and reusable catalyst for selective oxidation of sulfides with H2O2
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Peroxotungstates held in a series of different supported ionic liquid brush catalysts were synthesized and characterized. Their catalytic performance towards the selective oxidation of sulfides with aqueous hydrogen peroxide was investigated under mild conditions. We found that the catalytic activities of the different catalysts depend on the number of supported ionic liquid layers and N-end-capped alkyl group on the imidazole ring. The highest yield of methyl phenyl sulfoxide was obtained using the BisILs-C8H17-W2 catalyst under optimum conditions. The sulfides were selectively oxidized to sulfoxides in high yields with trace sulfones detected by GC upon using 1.1 equivalents of H2O2. At 2.5 equivalents of H 2O2 the sulfones were found to be the main products. It is noteworthy that the catalyst resulted in high chemoselectivity towards sulfur groups with unsaturated double bonds even though excess hydrogen peroxide was used in addition to exhibiting high catalytic activity. There was no apparent loss of catalytic efficiency until the 8th cycle.
- Shi, Xianying,Han, Xiaoyan,Ma, Wenjuan,Wei, Junfa,Li, Jing,Zhang, Qiang,Chen, Zhanguo
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- Two Ce3+-Substituted Selenotungstates Regulated by N, N-Dimethylethanolamine and Dimethylamine Hydrochloride
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Two multi-Ce3+-substituted selenotungstates (STs), [HDMEA][H2N(CH3)2]4H3Na4[Ce2(H2O)6(DMEA)W4O9(α-SeW9O33)3]·26H2O (1) and [H2N(CH3)2]10H4Na10[Ce2W4O9(H2O)7(α-SeW9O33)3]2·63H2O (2), were prepared by the one-pot approach of sodium tungstate, sodium selenite, and lanthanide nitrate in an acidic water solution in the presence of N,N-dimethylethanolamine (DMEA) or dimethylamine hydrochloride (DMAHC). 1 was obained in the presence of DMEA, whereas 2 was synthesized in the presence of DMAHC. The trimeric polyoxoanion of 1 contains an unusual V-shaped [Se3W29O103]20- group embracing a prominent heterometal oxide fragment, [Ce2(H2O)6(DMEA)W2O5]8+, and the hexameric polyoxoanion of 2 is constructed from two equivalent trimeric [Ce2W4O9(H2O)7(SeW9O33)3]2 24- subunits through two -O-W-O-Ce-O- linkages. The most worthy of attention is that the polyoxoanion of 1 can be approximatively viewed as a half of the polyoxoanion of 2 because of the coordination and blocking effect of DMEA. The stability of 1 and 2 in different water pH values was studied by electrospray ionization mass spectroscopy (ESI-MS), and the results manifest that 1 and 2 are stable in pH = 3.5-7.5 and 3.5-7.0, respectively. The oxidation reactions of aromatic sulfides catalyzed by H2O2 were studied when 1 or 2 worked as a catalyst, and experimental results reveal that 1 or 2 can serve as available catalysts for the oxidation of aromatic sulfides under mild conditions.
- Li, Hai-Lou,Lian, Chen,Chen, Li-Juan,Zhao, Jun-Wei,Yang, Guo-Yu
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- First-row early transition metal complexes with a highly sterically demanding triisopropylphenyl amino triphenolate ligand: Synthesis and applications
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Amino triphenolate ligands have been widely used for the synthesis of various transition metal complexes aiming at various applications such as ring-opening polymerization, olefin polymerization, and sulfoxidation. However, the introduction of highly ster
- Bae, Dae Young,Park, Gyeong Su,Ko, Nakeun,Son, Kyung-Sun,Lee, Eunsung
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- High Chemoselectivity in the Construction of Aryl Methyl Sulfones via an Unexpected C-S Bond Formation between Sulfonylhydrazides and Dimethyl Phosphite
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A highly chemoselective route to aryl methyl sulfones via an unexpected C S bond formation between sulfonylhydrazides and dimethyl phosphite catalyzed by NaI under mild conditions has been established. This transformation provides an alternative and metal-free pathway to acquire various aryl methyl sulfones in good to excellent yields. Notably, dimethyl phosphite was employed as a stable and readily available alkyl source.
- Liu, Teng,Yu, Shiwen,Shen, Xiang,Li, Yixian,Liu, Jianjun,Huang, Chao,Cheng, Feixiang
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p. 153 - 160
(2021/10/04)
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- Polyoxometalate-Based Organic-Inorganic Hybrids as Heterogeneous Catalysts for Cycloaddition of CO2with Epoxides and Oxidative Desulfurization Reactions
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Self-assembly of polyoxometalates, transition metal salts, and 2,6-bis(2′-pyridyl)-4-hydroxypyridine (LOH) obtained four organic-inorganic hybrids [Co2.5(LOH)(LO)2(H2O)2(PW12O39)]·3CH3CN·2OH (1), [Zn1.5(LOH)3]·(PMo12O40)·CH3OH·2H2O (2), [Cd1.5(LOH)3]·(PW12O40)·2CH3OH·1.5H2O (3), and [Mn(LOH)2]·(PW12O40)·2CH3CN·H3O (4). Hybrid 1 exhibits an extended chain, which could be further connected into a 3D supramolecular architecture by H-bonds. Hybrids 2-4 feature monomolecular structures, which are further bridged via H-bonds to yield charming 3D supramolecular structures. Noteworthy, 1 and 2 can be employed as recyclable and highly efficient heterogeneous catalysts. The activated 1 displays a high catalytic activity for the cycloaddition reaction of CO2 and epoxides. Hybrid 2 exhibits an excellent catalytic performance for the oxidative desulfurization reaction.
- Zhao, Yu-Qing,Liu, Ying-Ying,Ma, Jian-Fang
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p. 1019 - 1027
(2021/01/13)
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- Self-Assembled Polyoxometalate-Based Metal-Organic Polyhedra as an Effective Heterogeneous Catalyst for Oxidation of Sulfide
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Two polyoxovanadate-based metal-organic polyhedra with octahedral (oct) and rhombic dodecahedral (rdo) geometries have been constructed from a concave molecular building block and linear and triangular carboxylate ligands. VMOP-7 is constructed from {V5O9Cl} SBU and a linear anthracene-9,10-dicarboxylic acid ligand in which all the anthracene groups are perpendicular to the edge of the octahedron. Such an arrangement mode can effectively reduce the steric hindrance between ligands. VMOP-8 is constructed from {V5O9Cl} SBU and a triangular biphenyl 3,4,5-tricarboxylate ligand, which exhibits an elongated rhombic dodecahedral configuration due to the geometry of the ligand. Furthermore, VMOP-8 can serve as a heterogeneous catalyst and exhibits efficient and common catalytic activity for oxidative desulfurization.
- Gan, Hong-Mei,Qin, Chao,Zhao, Liang,Sun, Chunyi,Wang, Xing-Long,Su, Zhong-Min
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p. 1028 - 1034
(2021/01/26)
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- Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts
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Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O (1), [Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMo12O40]3?/[PW12O40]3?anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMo12O40]3?anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that1and3as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.
- Li, Jie,Du, Peng,Liu, Ying-Ying,Ma, Jian-Fang
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supporting information
p. 1349 - 1356
(2021/02/09)
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- Tetrameric Lanthanide-Substituted Silicotungstate {Ln8Si4W40} Nanoclusters: Synthesis, Structural Characterization, Electrochemistry, and Catalytic Application for Oxidation of Thioethers
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All the title nanoclusters 1–10 with the molecular formula [(Ln2SiW10O38)4(W3O8)(OH)4(H2O)2]26? [LnIII =Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Tm (8), Yb (9), and Y (10)] have been synthesized and isolated as mixed sodium and potassium salts. These nanoclusters are characterized by various analytical techniques such as FT-IR, UV/Vis, Photoluminescence, Single crystal X-ray diffraction, Electrochemistry, ICP-AES and Thermogravimetric analysis, and Powder X-ray diffraction. The {Ln8Si4W40} complexes show high efficiency and selectivity for the oxidation of thioethers using H2O2 as green oxidant. It is worth mentioning that the catalyst can be recovered even after five cycles of reaction with only a slight loss in its activity.
- Khan, Imran,Das, Vivek,Teillout, Anne-Lucie,Mbomekallé, Isra?l-Martyr,de Oliveira, Pedro,Sahoo, Subash Chandra,Hussain, Firasat
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supporting information
p. 1071 - 1081
(2021/03/16)
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- Air atmospheric photocatalytic oxidation by ultrathin C,N-TiO2nanosheets
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Herein, we demonstrate the highly efficient photocatalytic sulfide oxidation reaction under mild conditions,i.e.in air, at room temperature and in the absence of a sacrificial reagent, co-catalyst or redox mediator, by using ultrathin C,N-TiO2nanosheets as a photocatalyst.
- Cheng, Xiuyan,Zhang, Jianling,Liu, Lifei,Zheng, Lirong,Zhang, Fanyu,Duan, Ran,Sha, Yufei,Su, Zhuizhui,Xie, Fei
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supporting information
p. 1165 - 1170
(2021/02/26)
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- A {Ti6W4}-Cluster-Substituted Polyoxotungstate: Synthesis, Structure, and Catalytic Oxidation Properties
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A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [H2N(CH3)2]3Na4H9[{Ti6W4O18(OH)(H2O)3}(B-α-SbW9O33)3]·20H2O (1), has been made by hydrothermal reactions of trivacant [B-α-SbW9O33]9- units, Ti4+ cations, and WO42- anions in the presence of [H2N(CH3)2]·Cl and structurally characterized. Intriguingly, the polyoxoanion of 1 is constructed from three [B-α-SbW9O33]9- units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [Ti6W4O18(OH)(H2O)3]11+ ({Ti6W4}) that is comprised of an octahedral [Ti6WO6(H2O)3]18+ cluster and an edge-sharing [W3O12(OH)]7- fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that 1 possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant H2O2.
- Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
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supporting information
p. 14622 - 14628
(2021/10/01)
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- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
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supporting information
p. 10314 - 10318
(2021/12/17)
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- A μ-AsO4-Bridging Hexadecanuclear Ni-Substituted Polyoxotungstate
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A novel tetrahedral μ-AsO4-bridging hexadecanuclear Ni-substituted silicotungstate (ST) Na21H10[(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]·60H2O (1) was made by the reactions of trivacant [A-α-SiW9O34]10- ({SiW9}) units with Ni2+ cations and Na3AsO4·12H2O and characterized by IR spectrometry, elemental analysis, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). 1 contains a novel polyoxoanion [(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]31- built by four trivacant Keggin [A-α-SiW9O34]10- fragments linked through an unprecedented [(AsO4){Ni8(OH)6(H2O)2(CO3)2}2]9+ cluster, where the tetrahedral AsO4 acts as an exclusively μ2-bridging unit to link multiple Ni centers; such a connection mode appears for the first time in polyoxometalate chemistry. Furthermore, the electrochemical and catalytic oxidation properties of compound 1 have been investigated.
- Lian, Chen,Li, Hai-Lou,Yang, Guo-Yu
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p. 3996 - 4003
(2021/04/07)
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- Single-Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11? Tungstophosphate Nanoclusters
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A series of eleven lanthanide containing di-Zinc (II) substituted heterometallic 3d–4f sandwich-type tungstophosphate nanoclusters [Ln{PZn2W10O38(H2O)2}2]11? (Ln=NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) have been synthesized by a single step reaction procedure. These clusters were characterized by various analytical techniques such as single crystal X-ray diffraction (SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-resolution electro-spray ionization mass spectrometry (HR-ESI-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), solid UV/Vis, photoluminescence spectroscopy, powder X-ray diffraction (P-XRD) and thermogravimetric analysis (TGA). All the polyanions are isostructural and consists of a lanthanide ion sandwiched between two units of (1,5) isomer of di-Zn substituted α-Keggin type tungstophosphate. The complexes Sm-2 a, Eu-3 a, Tb-5 a, and Dy-6 a show good photoluminescence behavior. The catalytic properties were examined for the oxidation of thioethers. The catalyst is stable with a high turn over frequency (TOF) of 6250 h?1 and can be recovered even after 5 consecutive cycles. Furthermore, magnetic properties revealed that Gd-4 a, Tb-5 a, Dy-6 a, Er-8 a, and Yb-10 a show single-molecule magnetic properties.
- Das, Vivek,Khan, Imran,Hussain, Firasat,Sadakane, Masahiro,Tsunoji, Nao,Ichihashi, Katsuya,Kato, Chisato,Inoue, Katsuya,Nishihara, Sadafumi
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p. 3819 - 3831
(2021/09/22)
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- {Ti6}/{Ti10} Wheel Cluster Substituted Silicotungstate Aggregates
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Two novel Ti-oxo wheel cluster substituted silicotungstates (STs) [H2N(CH3)2]9H9[Ti6O6(SiW10O37)3]·11H2O (1) and [H2N(CH3)2]16H10[Ti10O11(SiW10O37)2(SiW9O35)2]·14H2O (2) have been made by hydrothermal reactions. The polyoxoanion of 1 is a ring-shaped trimer where a Ti6O6 ({Ti6}) wheel cluster is encapsulated by three divacant [SiW10O37]10- (SiW10O37) fragments. However, 2 is built by two divacant SiW10O37 units and two rare trivacant [SiW9O35]12- (SiW9O35) fragments and further installs an unprecedented Ti10O11 ({Ti10}) double-wheel cluster. To the best of our knowledge, 2 is rare in POM chemistry. Studies on the catalytic oxidation properties reveal that 1 exhibits high catalytic activity toward the oxidation of various sulfides using H2O2 as an oxidant. Furthermore, 1 can be facilely recycled and reused for at least five cycles without obvious loss of catalytic activity.
- Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
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p. 16852 - 16859
(2021/11/13)
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- Method for synthesizing sulfone compounds under photocatalysis condition
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for synthesizing sulfone compounds under a photocatalysis condition. Aromatic hydrazine and sulfinate are used as raw materials, and under the action of alkali and a solvent, a sulfone compound is generated through reaction under the condition of air or oxygen under the illumination of visible light. According to the method disclosed by the invention, aryl hydrazine is used as an arylation reagent, polyacid salt is used as a catalyst or an organic photosensitizer is used as a catalyst, and the sulfones compound can be efficiently synthesized by coupling with sulfinate under the condition of room temperature through visible light irradiation. The method has good substrate universalityand relatively mild reaction conditions, is not only a substitute for synthesizing sulfone compounds by coupling from simple substrates reported at present, but also broadens the new application of the polyacid salt in the field of photocatalysis.
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Paragraph 0064-0069
(2021/03/31)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
- Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
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supporting information
p. 3896 - 3905
(2020/07/09)
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- Two polyoxometalate-based inorganic-organic hybrids and one coordination polymer assembled with a functionalized calix[4]arene: Catalytic and electrochemical properties
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Self-assembly of 4-pyridyl-functionalized calix[4]arene ligand 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27,28-tetrakis[(4-pyridylmethyl)oxy]calix[4]arene (L), Ag(I)/Cd(II) cations and polyoxometalate obtained two inorganic-organic hybrids [Ag3(L)2][PMo12O40]·CH3CN·4H2O (1), [Ag3(L)2][PMo12O40]·2DMA·0.5EtOH (2) and one complex [Cd3(L)2Cl6]·4CH3CN·4H2O (3) (DMA = N,N-dimethylacetamide). Hybrids 1 and 2 have fascinating one-dimensional chains, which are linked by hydrogen bonds between the C atoms of L ligands and the O atoms of [PMo12O40]3? anions to generate supramolecular layers. 3 displays a thick layer containing trinuclear Cd(II) clusters. Noteworthy, hybrid 1 exhibits excellent heterogeneous catalytic activity for oxidative desulfurization reaction and obvious electrocatalytic activity for oxidize ascorbic acid and reduce NaBrO3. Complex 3 shows heterogeneous catalytic ability for Knoevenagel condensation reaction.
- Li, Zhuo,Liu, Ying-Ying,Xu, Guo-Hai,Ma, Jian-Fang
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- Sulfoxidation inside a hypercrosslinked microporous network nanotube catalyst
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In the present work, a kind of efficient heterogeneous catalyst was synthesized from amine-functionalized hypercrosslinked bottlebrush copolymers of microporous network nanotubes (amine-MNNs) and Na2WO4. The synthesized tungstate-supported microporous network nanotubes (TMNNs) catalyst was shown to be highly active in the selective H2O2 oxidation of sulfides to sulfoxides or sulfones under mild conditions due to the high specific surface area (800 m2 g-1) and firm structure of the nanotubes. The catalyst was found to be very stable and could be recycled at least 8 times without any significant loss of activity. These results present a new opportunity for the development of efficient green organic catalytic materials with high activity.
- Shi, Zhaocheng,Ying, Zhong,Yang, Liusai,Meng, Xiaoyan,Wu, Lidan,Yu, Leshu,Huang, Sen,Xiong, Linfeng
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supporting information
p. 1542 - 1547
(2020/02/06)
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- Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate-Resorcin[4]arene-Based Metal-Organic Materials
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The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic-organic hybrid materials, namely, [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1-3, the [M(TMR4A)(H2O)4]2+ species (M = MnII, NiII, ZnII) and [Mo6O19]2- anions are held together via C-H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+ cations were linked by one [β-Mo8O26]4- anion to produce an attractive molecular dimer. Remarkably, 1-4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.
- Guo, Ting-Ting,Ma, Jian-Fang,Yang, Jin,Yu, Ming-Yue
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supporting information
(2020/04/02)
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- Accurate Regulating of Visible-Light Absorption in Polyoxotitanate-Calix[8]arene Systems by Ligand Modification
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With use of a macrocyclic polyphenol, tert-butylcalix[8]arene (TBC[8]), as ligands, a series of TBC[8]-stabilized {Ti4O2}clusters, containing penta- and hexacoordinated Ti centers, were synthesized. Such complexes are "core-shell" shaped containing a {Ti4O2} core arranged in a zigzag fashion. While outer walls of the clusters are decorated by deprotonated TBC[8], their upper and lower surfaces can be modified by various O- or N-donor ligands, and the ratio of the penta- and hexacoordinated Ti(IV) centers in the {Ti4O2} core can be precisely regulated from 4:0, to 3:1, to 2:2, to 1:3, and finally to 0:4. The combined coordination of different ligands in the axial direction shows significant influence on the adsorption of the TBC[8]-Ti4 system in the visible-light region, and their absorption edge can be precisely regulated from 600 to 700 nm. The above structural functionalization in the TBC[8]-Ti4 system also tunes their photocatalytic H2 production activities and oxidative desulfurization ability. Thus, for the first time, by confining the polyoxotitanium cluster in macrocyclic molecules, we provide an example of understanding the structure-property relationship of titanium-oxygen materials by ligand modification.
- Liu, Chao,Yang, Xin-Xue,Yi, Xiao-Yi,Yu, Wei-Dong
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- A Nanosized Propeller-like Polyoxometalate-linked Copper(I)-Resorcin[4]arene for Efficient Catalysis
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The design and assembly of polyoxometalate-resorcin[4]arene-based metal-organic molecular materials are particularly attractive for their elegant structures and potential functions. By applying a newly designed resorcin[4]arene ligand (TPC4R-II), a copper(I)-coordinated polyoxometalate-based metal-organic molecular material, namely, [CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1), was rationally assembled. Three copper(I)-coordinated resorcin[4]arenes are held together by a central [PMo12O40]3- to yield a supramolecular propeller. 1 features efficient catalytic performances for oxidation desulfurization (ODS) and azide-alkyne cycloaddition (AAC) reactions. This work affords a feasible method for the nanosized polyoxometalate-based metal-resorcin[4]arene assemblies by well combinating two types of large composites as well as low coordination metal cations.
- Guo, Ting-Ting,Ma, Jian-Fang,Xiong, Yan-Ling,Yang, Jin,Yu, Ming-Yue
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supporting information
p. 15402 - 15409
(2020/11/02)
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- Copper(ii)-containing tungstotellurates(vi): Syntheses, structures and their catalytic performances in selective oxidation of thioethers
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We report the syntheses and structures of two new copper(ii)-containing tungstotellurates(vi) Na12[TeVI2W8O38Cu2(H2O)2]·7H2O (Te2W8Cu2) and Na6[TeVIW6O24Cu(NH2CH2CO2)2]·6H2O (TeW6Cu). The two compounds were synthesized by a simple one-pot method and characterized by single-crystal X-ray diffraction (XRD), powder XRD, FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis in the solid state. Furthermore, their catalytic properties for the selective oxidation of thioethers were also studied systematically. The catalytic experiment results indicate that the tungstotellurate(vi) Te2W8Cu2 is an effective heterogeneous catalyst for the selective oxidation of thioethers to sulfoxides or sulfones by an H2O2 oxidant at room temperature. Under the ambient conditions, Te2W8Cu2 can convert 99percent of methyl(phenyl)sulfane to sulfoxides or sulfones with 96percent or 99percent selectivity, respectively, and the utilization rate of H2O2 is up to 80percent. Furthermore, Te2W8Cu2 as a heterogeneous catalyst is stable in the reaction and could be reused at least five cycles with conserved activity.
- Hu, Changwen,Li, Peihe,Li, Xuanyao,Lin, Zhengguo,Liu, Jinghai
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p. 22515 - 22521
(2020/07/03)
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
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supporting information
p. 433 - 438
(2020/02/13)
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- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
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p. 2991 - 2992
(2020/03/24)
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- Three Zr(IV)-Substituted Polyoxotungstate Aggregates: Structural Transformation from Tungstoantimonate to Tungstophosphate Induced by pH
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Three novel Zr-substituted polyoxotungstate aggregates [H2N(CH3)2]7NaH2[Zr2Sb2O3(A-α-PW9O34)2]·16H2O (1), [H2N(CH3)2]6H12[ZrSb4(OH)O2(A-α-PW8O32)(A-α-PW9O34)]2·33H2O (2), and [H2N(CH3)2]4Na11.5H4.5[Zr4W8Sb4P5O49(OH)5(B-α-SbW9O33)2]·53H2O (3) have been made in hydrothermal reactions of the [B-α-SbW9O33]9- precursor with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and sodium acetate buffer (pH = 4.8) and structurally characterized. Different pH values induce structural transformation from tungstoantimonate (TA) to tungstophosphate (TP). 1 is a di-Zr-substituted sandwich-type TP, the tetranuclear heterometallic [Zr2Sb2O3]8+ entity sandwiched by two [A-α-PW9O34]9- moieties. 2 is a double sandwich-type structure, which can be perceived as two equivalent sandwiched [Sb3(PW8O32)(PW9O34)]11- further sandwiching one [Sb2Zr2(OH)2O4]4+ core to form a novel large-size sandwich-type architecture. Different from 1 and 2, 3 is a tetra-Zr-substituted sandwiched configuration, in which two [B-α-SbW9O33]9- fragments sandwich a unique 21-core Sb-P-W-Zr oxo cluster ({Zr4W8Sb4P5}). Furthermore, the catalytic oxidation of aromatic thioethers by 3 as the heterogeneous catalyst has been investigated, showing high conversion and remarkable selectivity as well as excellent recyclability.
- Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu,Yin, Da-Peng
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p. 12842 - 12849
(2020/09/15)
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- Synthesis of Na22[((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2] [(RE)III = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb]: Synthesis, characterization and catalytic application
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A series of eight rare-earth substituted antimony tungstates with the formulae [((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2]22– [(RE)III = Y(1), Gd(2), Tb(3), Dy(4), Ho(5), Er(6), Tm(7), Yb(8)] has been synthesized under ambient conditions. The compounds were isolated using rare-earth salts and Na9[B-α-SbW9O33]?19.5 H2O as precursors along with sodium dihydrogen phosphate in 1 M NaCl solution. The addition of dihydrogen phosphate was found to be a crucial step for the isolation of these polyanions. The polyanions were characterized by various analytical techniques such as single crystal X-ray diffraction (1a – 6a) (SC-XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The compounds were found to show efficient heterogeneous catalytic activity for oxidation of thioethers.
- Gupta, Rakesh,Hussain, Firasat,Kaushik, Reetam,Khan, Imran
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- Inorganic-organic hybrid polyoxovanadates based on [V4O12]4-or [VO3]22-clusters: Controllable synthesis, crystal structures and catalytic properties in selective oxidation of sulfides
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By rationally controlling hydrothermal conditions, three new inorganic-organic hybrid polyoxovanadates (POVs) [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole) have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar structures including [V4O12]4- clusters; complex 3, however, was isolated as a structure by including the [VO3]22- cluster under a different synthetic condition compared with those of 1 and 2. Both complexes 1 and 2 display an interesting 3D supramolecular structure, and complex 3 shows a 2D two parallel networks supramolecular structure linked by a [Co2O2] unit due to the different coordination environments of the central metals. Three inorganic-organic hybrid POVs asheterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with high conversion and high selectivity (up to 99.5 for sulfoxides and 98.5% for sulfones respectively catalyzed by 1). Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant) abatement with high activity and selectivity towardthe corresponding sulfoxide. Moreover, complex 1 can be reused at least three times in sulfoxidationreactions without losing its activity.
- Guo, Daigaojie,Han, Yinfeng,He, Guofang,Hu, Changwen,Huang, Xianqiang,Li, Jikun,Wang, Congcong,Wei, Chuanping,Zhang, Jianping
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p. 14148 - 14157
(2020/11/02)
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- A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers
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A neoteric hepta-nuclear Ti-oxo-cluster-substituted tetrameric tungstoantimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2·124H2O (1) has hydrothermally been synthesized and tested by single-crystal/powder X-ray diffraction, IR spectra, and thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon hepta-nuclear Ti-oxo-cluster octahedron [Ti7O6]16+ enclosed in four [B-α-SbW9O33]9- building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with H2O2 for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability and excellent recyclability.
- Li, Hai-Lou,Lian, Chen,Yin, Da-Peng,Jia, Zhi-Yu,Yang, Guo-Yu
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p. 376 - 380
(2019/01/09)
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- Highly stable polyoxometalate-resorcin[4]arene-based inorganic-organic complexes for catalytic oxidation desulfurization
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Self-assembly of a resorcin[4]arene-based ligand (TMR4A) with metal salts and H3PMo12O40·xH2O offers two isostructural complexes, namely, [Ni2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (1) and [Co2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (2). In both 1 and 2, one Cl? anion bridges two metal cations, and each metal cation is further chelated by four 2-mercaptopyridine N-oxide groups of one TMR4A, producing a [M2Cl(TMR4A)2]3+ dimer (M?=?Ni or Co). The negative [PMo12O40]3? as a counter-anion balances the positive charge. Markedly, 1 and 2 exhibit high stability in aqueous solutions with different pH values and in organic solvents. Remarkably, the efficient heterogeneous catalytic capability for oxidative desulfurization was studied by suing 1 and 2 as recycled catalysts. Moreover, the electrochemical behaviors of the two compounds were discussed as well.
- Yu, Ming-Yue,Yang, Jin,Xu, Xianxiu,Ma, Jian-Fang,Wang, Zhenxing
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- Sodium sulfate-hydrogen peroxide-sodium chloride adduct: selective protocol for the oxidative bromination, iodination and temperature dependent oxidation of sulfides to sulfoxides and sulfones
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The regioselective bromination and iodination of unprotected aromatic primary amines using enclathrated hydrogen peroxide as an oxidant under mild conditions has been developed, in which potassium bromide (KBr) and potassium iodide (KI) were used as brominating and iodinating agents, respectively. The adduct shows not only regioselectivity for para- or ortho-isomers but also a remarkable chemoselectivity for monobromination. Selective oxidation of sulfides to sulfoxides and sulfones has also been studied and good to excellent yields of the desired products were obtained. Acetic acid was found to be the solvent of choice for these reactions. This simple method represents an ecologically benign and alternative pathway for the oxidative halogenation of anilines and the oxidation of sulfides to sulfoxides and sulfones.
- Gayakwad, Eknath M.,Patel, Khushbu P.,Shankarling, Ganapati S.
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supporting information
p. 6001 - 6009
(2019/04/17)
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- Method for photocatalytic synthesis of sulfur sulfone compounds
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The invention discloses a method for photocatalytic synthesis of sulfur sulfone compounds, and belongs to the technical field of catalysis. The invention provides a novel green environmentally-friendly method to efficiently synthesize the sulfur sulfone derivatives, and one thioether compound and an oxidizing agent are subjected to direct oxidization to form one corresponding sulfur sulfone compound under illumination by utilizing cercosporin as a catalyst. The method provided by the invention adopts the cercosporin as the catalyst, the catalytic conditions are milder, the reaction can be performed at room temperature under visible light irradiation, the catalyst has high catalytic activity and can be used for high-selectivity catalytic synthesis of the sulfur sulfone compounds, and the micro catalyst can make a yield higher, wherein the yield can reach 90% or more; and the photocatalyst and substrate raw materials used in the method are simple and easy to obtain, have low costs and can be produced on a large scale, and the method has very good application prospects.
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Paragraph 0040-0041
(2019/05/15)
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- Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
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The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0092-0095
(2019/02/13)
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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
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- An Oxalate-Functionalized Tetra-ZrIV-Substituted Sandwich-Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers
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A previously unknown inorganic–organic hybrid polyoxidometalate constructed from oxalate-functionalized tetra-ZrIV-substituted dimeric silicotungstate, (NH4)3Na5K6[Zr4(μ3-O)2(μ-OH)2(ox)2(SiW10O37)2]·23H2O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Compound 1 contains a centrosymmetric polyoxidoanion structure with two [SiW10O37]10– units sandwiching a [Zr4(μ3-O)2(μ-OH)2(ox)2]6+ cluster. The catalytic performances of 1 involving oxygenation reactions of thioethers by H2O2 were evaluated, showing that 1 is an excellent catalyst for the catalytic oxidation of thioethers to sulfoxides/sulfones.
- Wang, Yue-Lin,Zhang, Zhong,Li, Hai-Lou,Li, Xu-Yan,Yang, Guo-Yu
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p. 417 - 422
(2018/09/06)
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- A multifunctional Co-based metal-organic framework: heterogeneous catalysis, chemiluminescence sensing and moisture-dependent solvatochromism
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Crystalline materials with multi-catalytic applications are of great value to both fundamental research and practical applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst with high stability. Self-assembly of a flexible ligand, 4-(4-carboxybenzylamino)benzoic acid (H2CBBA), with Co(ii) resulted in a 3D framework, CBBA-Co, with Co3O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic process. In addition, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H2O2 in the range of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of employing MOFs as an efficient platform for the fabrication and study of multifunctional catalysts, both experimentally and theoretically.
- Xie, Ming-Hua,Wang, Ya,Li, Ruo-Fei,Dong, Peng-Yu,Hou, Gui-Hua,Shao, Rong,Xi, Xin-Guo,Guan, Rong-Feng,Yang, Xiu-Li
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p. 12406 - 12413
(2018/09/25)
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- An Efficient Oxidation of Sulfides to Sulfones with Urea-Hydrogen Peroxide in the Presence of Phthalic Anhydride in Ethyl Acetate
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A metal-free, environmentally benign oxidation of substituted sulfides directly to their corresponding sulfones is described. Using urea-hydrogen peroxide and phthalic anhydride in ethyl acetate clean conversion into the sulfone was achieved without observation of the possible sulfoxide oxidation product.
- Lutz, Marlon,Wenzler, Marta,Likhotvorik, Igor
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supporting information
p. 2231 - 2234
(2018/04/16)
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- Fe3O4/PEG-SO3H as a heterogeneous and magnetically-recyclable nanocatalyst for the oxidation of sulfides to sulfones or sulfoxides
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We present below a sulfonated-polyethylene glycol-coated Fe3O4 nanocomposite (Fe3O4/PEG-SO3H) as a greatly effective and ecological nanocatalyst for the selective oxidation of sulfides to sulfoxides or sulfones with brilliant yields under solvent-free conditions by employing 30% hydrogen peroxide as the oxidant. A number of sulfides containing alcohol, ester, and aldehyde functional groups were fruitfully and selectively oxidized without altering the desired characteristics. The magnetic nanocatalyst (Fe3O4/PEG-SO3H) can be conveniently and swiftly retrieved through the utilization of an external magnetic tool and recycled for more than 10 reaction runs without significantly decreasing its catalytic behavior.
- Mirfakhraei, Saeideh,Hekmati, Malak,Eshbala, Fereshteh Hosseini,Veisi, Hojat
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p. 1757 - 1761
(2018/02/09)
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- A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
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The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
- Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
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p. 6589 - 6599
(2018/05/31)
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- Synthesis, Characterization and Catalytic Activity of a Tungsten(VI) Amino Triphenolate Complex
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Abstract: Synthesis, characterization and catalytic activity of a novel tungsten(VI) amino triphenolate complex have been investigated. In particular, a tungsten(VI) amino triphenolate complex has been synthesized and tested in the oxidation of sulfides and cyclooctene, using hydrogen peroxide as terminal oxidant. The catalyst has proved to be air and water tolerant, also showing a good efficiency in terms of yields and selectivity. Moreover, an upgrade of our previous ligand synthesis is herein reported. The new developed procedure allows to obtain the triphenolamine in large scale without the use of chromatography for the intermediates purification. Graphical Abstract: [Figure not available: see fulltext.].
- Badetti, Elena,Bonetto, Alessandro,Romano, Francesco,Marchiò, Luciano,Zonta, Cristiano,Licini, Giulia
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p. 2313 - 2318
(2017/08/22)
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- Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane Tetrachloro Manganate with Perovskite Type Structure
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Abstract: Layered 2D organic–inorganic hybrid perovskite (OIHS) of the diammonium series, 1,5 di-aminepentane tetrachloro mangenate ([NH3–(CH2)5–NH3] MnCl4) was prepared by slow evaporation and reducing temperature method and characterized by single crystal X-ray diffraction analysis. Its structure consists of organic cation, [NH3(CH2)5NH3]+2 extended in a zigzag fashion and inorganic anion, [MnCl6]?2 where Mn2+ is coordinated by six Cl? ion in octahedral fashion. The organic and inorganic segments are alternately stacked along c-axis where inorganic layer is extended through corner-shared octahedra sandwiched by the di-aminopentane molecules. The layers (organic and inorganic) were connected to each other through N–HCl hydrogen bonds and van-der Waals interaction to build cation–anion–cation cohesion. The hybrid crystal had orthorhombic non-centrosymetric system having I212121 space group with unit cell parameters a = 7.1742(3) ?, b = 7.3817(3) ?, c = 23.9650(10) ?, V = 1269.13 ?3 and Z = 4. The hybrid exhibited excellent catalytic activity towards sulphide and alkene oxidation using aqueous H2O2 as an oxidant. Graphical Abstract: OIHS of the diammonium series [NH3–(CH2)5–NH3] MnCl4; 1,5 di-aminepentane tetrachloro mangenate were prepared by slow evaporation and temperature decrease method, characterized by single crystal X-ray diffraction. This complex exhibits excellent catalytic activity towards sulphide oxidation and alkene oxidation using aqueous H2O2 as an oxidant. [Figure not available: see fulltext.].
- Mondal, Paramita,Abdel-Aal, Seham Kamal,Das, Debasis,Islam, Sk Manirul
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p. 2332 - 2339
(2017/08/22)
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- A Simple Metal Free Oxidation of Sulfide Compounds
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Abstract: This work reports simple, efficient, selective protocol for the oxidation of sulfide compounds. Various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones using H2O2as an oxidant in presence of catalytic amount of caprylic acid. The reaction proceeds at room temperature to give sulfoxide and by increasing the reaction temperature to 50 °C, this system provides selective formation of sulfone with high conversion and excellent yields. Green, convenient, easy work-up, chemoselectivity, broad substrate scope and regeneration of catalyst are the important highlights of this protocol. Graphical Abstract: [Figure not available: see fulltext.] Using H2O2as an oxidant in presence of catalytic amount of caprylic acid various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones.
- Wagh, Ravindra B.,Nagarkar, Jayashree M.
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p. 181 - 187
(2017/02/18)
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- Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant
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Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
- Kupwade,Khot,Lad,Desai,Wadgaonkar
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p. 6875 - 6888
(2017/10/06)
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- Schiff base complex of Mo supported on iron oxide magnetic nanoparticles (Fe3O4) as recoverable nanocatalyst for the selective oxidation of sulfides
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In this work, a new tridentate Schiff base dioxo-molybdenum(VI) complex immobilized on silica-coated magnetic nanoparticles (MoO25CML–Fe3O4@SiO2) has been synthesized and characterized using different techniques such as FTIR, TGA, AAS, ICP–AES, XRD, VSM, EDX and SEM analyses. The catalytic activity of synthesized complex was examined in the oxidation of various sulfides in the presence of H2O2 as cheap, green and eco-friendly oxidant. This catalytic system provides high conversion and selectivity toward either sulfoxides or sulfones under different conditions. Also, the nanocatalyst could be easily separated and regenerated from reaction media by external magnet and could be reused for ten times without significant loss of the activity and selectivity.
- Aghajani, Milad,Monadi, Niaz
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p. 963 - 975
(2017/03/11)
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- Copper-catalyzed: S -methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
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A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water smoothly without any ligand or additive under mild conditions and this catalyst-in-water can be recycled several times.
- Yang, Yu,Bao, Yajie,Guan, Qianqian,Sun, Qi,Zha, Zhenggen,Wang, Zhiyong
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p. 112 - 116
(2017/08/15)
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- Photoredox catalysis for oxygenation/deoxygenation between sulfides and sulfoxides by visible-light-responsive polyoxometalates
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In this paper, we report the unique visible-light-responsive photoredox catalysis of a divacant lacunary silicotungstate TBA4H4[γ-SiW10O36] (SiW10) for functional group transformations of sulfur-containing compounds; namely, (i) aerobic oxygenation of sulfides to sulfoxides and (ii) deoxygenation of sulfoxides to sulfides. In the presence of suitable additives, such as Ce3+ (electron transfer mediator for oxygenation) and an alcohol (electron and proton donor for deoxygenation), SiW10 shows visible-light-induced charge transfers by using the newly formed highest occupied molecular orbitals derived from the coordinating Ce3+ or alcohol at the vacant site of SiW10. Consequently, oxygenation of sulfides and deoxygenation of sulfoxides can selectively proceed by irradiation with visible light (λ > 400 nm) to afford the corresponding desired products in high yields. The SiW10 photocatalysts can readily be recovered and reused for these transformations. Based on evidence from several experiments, the roles of the additives as well as the reaction mechanisms for these transformations are also discussed.
- Suzuki, Kosuke,Jeong, Jinu,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 1014 - 1021
(2016/02/19)
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- Manganese- and Lanthanide-Based 1D Chiral Coordination Polymers as an Enantioselective Catalyst for Sulfoxidation
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The chiral 1D-coordination polymers (CP) {[Ln2(MnLCl)2(NO3)2(dmf)6(H2O)2]·xH2O}n [Ln = Pr (1), Nd (2), Sm (3), and Gd (4)] were synthesized by the reaction of N,N'-bis(4-carboxysalicylidene)cyclohexanediamine (H4L) with [MnCl2·4(H2O)] and [Ln(NO3)3·x(H2O)] in the presence of dmf/pyridine at 90 °C. The polymers consist of manganese-salen-based moieties having carboxylate linkers connected to rare earth atoms in a 1D-chain structure. The polymers are very easily accessible. A one-step synthesis for the ligand and a second step for the preparation of the 1D coordination polymers starting from commercially available material are needed. The solid state structures of 1-4 were established by single-crystal X-ray diffraction. Compounds 1-4 were investigated as heterogeneous catalysts for the sulfoxidation reaction of various alkyl and aryl sulfides. The influence of various solvents and oxidizing agents on the catalytic reaction was examined. It was found that the catalysts were active for more than one reaction cycle without significant loss of activity. For phenylsulfide with 1 mol % of the catalyst 4, a maximum conversion 100% and a chemoselectivity 88% were observed.
- Yadav, Munendra,Bhunia, Asamanjoy,Jana, Salil K.,Roesky, Peter W.
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supporting information
p. 2701 - 2708
(2016/04/05)
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