An efficient recyclable peroxometalate-based polymer-immobilised ionic liquid phase (PIILP) catalyst for hydrogen peroxide-mediated oxidation

Doherty, Simon; Knight, Julian G.; Ellison, Jack R.; Weekes, David M.; Harrington, Ross W.; Hardacre, Christopher; Manyar, Haresh

doi:10.1039/c2gc16679h

Cited by 54 publications

(34 citation statements)

References 21 publications

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“…Peroxometalate-based PIILP [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP (2) was prepared by stoichiometric exchange of the bromide anions in pyrrolidinium-based ROMP-derived polymer 1 with [PO 4 {WO(O 2 ) 2 } 4 ] 3-(Scheme 1) 30a and the resulting amorphous white solid that precipitated was characterized by a combination of solid state P-31 NMR spectroscopy, ICP-OES (tungsten content), nitrogen sorption analysis, TEM and TGA/DSC. A series of catalytic reactions was first conducted under batch conditions to evaluate the efficiency of 2 as a catalyst for sulfide oxidation and to undertake preliminary optimization studies and recycle experiments.…”

Section: Catalyst Synthesis Batch and Recycle Studiesmentioning

confidence: 99%

“…S43 1 H and 13 C{ 1 H} NMR spectra and mass spectra for oxidation sulfoxides and sulfones S58Figure S44FT-IR Spectra of (a) fresh[PO 4 {WO(O 2 ) 2 } 4 ]@PIILP(2) and(b) catalyst isolated after the 6 th run of a methanol recycle experimentS59 Figure S45 Conversion-selectivity profile as a function of temperature for the continuous flow [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalysed sulfoxidation of thioanisole in acetonitrile with a residence time of 4 min S60 Figure S46 Conversion-selectivity profile as a function of temperature for the continuous flow [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalysed sulfoxidation of thioanisole in methanol with a residence time of 4 min S61 Figure S47 Conversion-selectivity profile as a function of residence time for the [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalyzed sulfoxidation of thioanisole in acetonitrile at 30 °C Conversion-selectivity profile as a function of residence time for the [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalyzed sulfoxidation of thioanisole in acetonitrile at 30 °C Conversion-selectivity profile as a function of residence time for the [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalyzed sulfoxidation of thioanisole in acetonitrile at 30 °C with 6 equivalents of H 2 O 2 . S66 Figure S52 Conversion-selectivity profile as a function of residence time for the [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP-catalyzed sulfoxidation of thioanisole in acetonitrile at 30 °C with 12 equivalents of H 2 O 2 S67 Figure S53a,b Determination of rate constants for the formation of methyl phenyl sulfoxide (k a ) and methyl phenyl sulfone (k b ) in acetonitrile with 12 equivalents of H 2 O 2 by fitting the concentrationtime profile for the consumption of sulfide and the formation of product.…”

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Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

et al. 2015

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ARTICLE This journal isThe peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP has been prepared by an anion exchange of ring opening metathesisderived pyrrolidinium-decorated norbornene/cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46,428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst . IntroductionThe selective oxidation of sulfides is a challenging and technologically important process as sulfoxides and sulfones are versatile intermediates used in the synthesis of fine chemicals, bioactive compounds, agrochemicals, 1 as chiral auxiliaries 2 and most recently as ligands for transition metal asymmetric catalysis. 3 Moreover, sulfide oxidation is also the basis for the catalytic oxidative desulfurisation of crude oil in which sulfur compounds are removed by selective extraction of their sulfones into a polar solvent under much milder conditions than typically required for classical industrial catalytic hydrodesulfurization. 4 Sulfoxidations have traditionally employed either strong oxidants, (e.g. nitric acid or KMnO 4 ) which suffer numerous drawbacks such as low yields, extreme reaction conditions and poor E-factors, 5 or reagents such as mchloroperbenzoic acid, 6 UHP, 7 NaClO, 8 NaIO 4 , 9 oxone 10 and dimethyldioxirane 11 which are expensive, must be used in excess, generate stoichiometric amounts of by-product and involve protocols that require long reaction times, high temperatures and complicated handling procedures. Since hydrogen peroxide is economical, more environmentally benign and relatively atom efficient it is considered the oxidant of choice and as such numerous organocatalysts, 12 enzymes 13 as well as transition metal catalysts based on iron, 14 manganese, 15 vanadium, 16 titanium, 17 ruthenium, 18 molybdenum, 19 tungsten, 20 and zinc 21 have been developed for this process. In this regard, an efficient catalyst must be highly selective for either sulfone or sulfoxide, inexpensive, easy to prepare and handle, operate under mild conditions across a wide range of substrates and functionality, have long term stability and be easy to recover and recycle. While several of these criteria have been successfully realized there is still a demand to identify and develop alternative systems to address remaining drawbacks ...

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Section: Catalyst Synthesis Batch and Recycle Studiesmentioning

confidence: 99%

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confidence: 99%

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

et al. 2015

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“…For the catalysts POSS-IL 8 -PW containing different IL, POSS-BIM 8 - 15 PW having a C4 hydrophobic tail displays a 90% conversion (entry 8), which is lower than those of the catalysts POSS-OIM 8 -PW, POSS-DIM 8 -PW and POSS-HIM 8 -PW carrying C8, C12, and C16 alkyl chain, respectively (entries 5, 9 and 10). Also notably, for the POSS-free samples containing different IL, the 20 increase of the length of alkyl chain in IL leads to continuous increase in the catalytic conversion from 45% to 80% (entries [11][12][13][14]. However, they are much lower than those of the POSScontaining ones.…”

Section: Catalytic Activity In the Epoxidation Reactionmentioning

confidence: 99%

POSS-derived mesoporous ionic copolymer–polyoxometalate catalysts with a surfactant function for epoxidation reactions

et al. 2016

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A series of novel polyoxometalate (POM)-based stable polymeric hybrids were successfully synthesized using polyhedral oligomeric vinylsilsesquioxanes (POSS) and ionic liquids (IL) bearing hydrophobic alkyl chains as the building blocks, followed by ion exchange with Keggin-type phosphotungstic acid (PW). The obtained hybrids POSS-ILx-PW were demonstrated to be mesostructured and amphiphilic materials with good thermal stability. Catalytic tests for H 2 O 2 -based epoxidation of cyclooctene have 10 shown that these newly designed catalysts exhibit extraordinary catalytic activities, catalytic rate, and quite stable reusability. The unique amphiphilic property and the mesoporous structure are revealed to be responsible for the catalysts' excellent performance in epoxidation reactions with H 2 O 2 .

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“…Due to these evident advantages, PW 4 has received significant attention as an active component for construction of heterogeneous epoxidation catalysts (Neumann and Miller, 1995;Neumann and Cohen, 1997;Hoegaerts et al, 2000;Sakamoto and Pac, 2000;Sels et al, 2000;Kovalchuk et al, 2007;Sofia et al, 2009;Maksimchuk et al, 2010;Leng et al, 2011;Doherty et al, 2012;Swalus et al, 2013;Nojima et al, 2015;Peng et al, 2016;Masteri-Farahani and Modarres, 2017;Shen et al, 2017;You et al, 2018). Silica modified by various cationic functional groups was widely used as support for immobilization of PW 4 (Neumann and Miller, 1995;Neumann and Cohen, 1997;Hoegaerts et al, 2000;Sakamoto and Pac, 2000;Kovalchuk et al, 2007;Sofia et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

“…Some of the SiO 2 -supported catalysts were prone to leaching and/or had a poor recyclability Kovalchuk et al, 2007) (sometimes information about reusability was not provided Neumann and Miller, 1995;Sakamoto and Pac, 2000). Several catalysts based on ion-exchange organic polymers and PW 4 have been developed Doherty et al, 2012;Swalus et al, 2013;Peng et al, 2016;Shen et al, 2017;You et al, 2018). In general, catalysts PW 4 /polymer showed high selectivity for epoxides and most of them could be recycled without a decrease in attainable conversion and selectivity Swalus et al, 2013;Peng et al, 2016;Shen et al, 2017;You et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

Carbon Nanotubes Modified by Venturello Complex as Highly Efficient Catalysts for Alkene and Thioethers Oxidation With Hydrogen Peroxide

et al. 2019

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In this work, we elaborated heterogeneous catalysts on the basis of the Venturello complex [PO 4 {WO(O 2 ) 2 } 4 ] 3− (PW 4 ) and nitrogen-free or nitrogen-doped carbon nanotubes (CNTs or N-CNTs) for epoxidation of alkenes and sulfoxidation of thioethers with aqueous hydrogen peroxide. Catalysts PW 4 /CNTs and PW 4 /N-CNTs (1.8 at. % N) containing 5-15 wt. % of PW 4 and differing in acidity have been prepared and characterized by elemental analysis, N 2 adsorption, IR spectroscopy, HR-TEM, and HAADF-STEM. Studies by STEM in HAADF mode revealed a quasi-molecular dispersion of PW 4 on the surface of CNTs. The addition of acid during the immobilization is not obligatory to ensure site isolation and strong binding of PW 4 on the surface of CNTs, but it allows one to increase the PW 4 loading and affects both catalytic activity and product selectivity. Catalytic performance of the supported PW 4 catalysts was evaluated in H 2 O 2 -based oxidation of two model substrates, cyclooctene and methyl phenyl sulfide, under mild conditions (25-50 • C). The best results in terms of activity and selectivity were obtained using PW 4 immobilized on N-free CNTs in acetonitrile or dimethyl carbonate as solvents. Catalysts PW 4 /CNTs can be applied for selective oxidation of a wide range of alkenes and thioethers provided a balance between activity and selectivity of the catalyst is tuned by a careful control of the amount of acid added during the immobilization of PW 4 . Selectivity, conversion, and turnover frequencies achieved in epoxidations over PW 4 /CNTs catalysts are close to those reported in the literature for homogeneous systems based on PW 4 . IR spectroscopy confirmed the retention of the Venturello structure after use in the catalytic reactions. The elaborated catalysts are stable to metal leaching, show a truly heterogeneous nature of the catalysis, can be easily recovered by filtration, regenerated by washing and evacuation, and then reused several times without loss of the catalytic performance.

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An efficient recyclable peroxometalate-based polymer-immobilised ionic liquid phase (PIILP) catalyst for hydrogen peroxide-mediated oxidation

Cited by 54 publications

References 21 publications

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

POSS-derived mesoporous ionic copolymer–polyoxometalate catalysts with a surfactant function for epoxidation reactions

Carbon Nanotubes Modified by Venturello Complex as Highly Efficient Catalysts for Alkene and Thioethers Oxidation With Hydrogen Peroxide

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