Journal of Molecular Catalysis A: Chemical最新文献

{"title":"Hydroformylation-hydrogenation and hydroformylation-acetalization reactions catalyzed by ruthenium complexes","authors":"Claudia Rodrigues ,&nbsp;Fabio G. Delolo ,&nbsp;Jakob Norinder ,&nbsp;Armin Börner ,&nbsp;André L. Bogado ,&nbsp;Alzir A. Batista","doi":"10.1016/j.molcata.2016.09.020","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.09.020","url":null,"abstract":"<div><p>In this work, the catalytic activity of ruthenium II and III complexes containing chloride, pyridine, phosphine and CO ligands was investigated in the hydroformylation – hydrogenation and hydroformylation – acetalization reactions. The complexes <em>mer-</em>[RuCl₃(dppb)(H₂O)]<strong>(1)</strong>, <em>mer-</em>[RuCl₃(dppb)(4-Vpy)]<strong>(2)</strong>, <em>mer-</em>[RuCl₃(dppb)(4-<em>t</em>Bupy)]<strong>(3)</strong>, <em>mer-</em>[RuCl₃(dppb)(py)]<strong>(4)</strong>, <em>mer-</em>[RuCl₃(dppb)(4-Phpy)]<strong>(5)</strong>, <em>mer-</em>[RuCl₃(dppb)(4-Mepy)]<strong>(6)</strong>, <em>cis-</em>[RuCl₂(CO)₂(dppb)]<strong>(7)</strong>, <em>trans-</em>[RuCl₂(CO)₂(dppb)]<strong>(8)</strong>, RuCl₃·xH₂O<strong>(9)</strong>, [RuCl₂(PPh₃)₃]<strong>(10)</strong> and [RuCl₂(PPh₃)₂(dppb)]<strong>(11)</strong> were used as supplied or synthesized as previously described in the literature {Where PPh₃ <!-->=<!--> <!-->triphenylphosphine, dppb<!--> <!-->=<!--> <!-->1,4-bis(diphenylphosphino)butane, py<!--> <!-->=<!--> <!-->pyridine, 4-Mepy<!--> <!-->=<!--> <!-->4-methylpyridine, 4-Vpy<!--> <!-->=<!--> <!-->4-vinylpyridine, 4-<em>t</em>Bupy<!--> <!-->=<!--> <!-->4-<em>tert</em>-butylpyridine and 4-Phpy<!--> <!-->=<!--> <!-->4-phenylpyridine}. These complexes were used as a pre-catalysts in a hydroformylation catalytic system to produce C<img>C, C<img>O and C<img>O bonds, where 1-decene resulted in a formation of respective alcohol and dimethyl acetals. Several reactions were performed in order to find the best reaction conditions presenting the best conversion (64% after 24<!--> <!-->h). The 1-decene was also used as a substrate in two type tandem reactions labeled as: hydroformylation – hydrogenation (HH) and hydroformylation – acetalization (HA) reactions. The relationship between Ru – catalyst/substrate was 1:100, without free ligands or additives, in a controlled temperature and pressure. All the products of catalytic reactions HH and HA were analyzed by CG-FID with good yields.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 586-592"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.09.020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2798706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic redox isomerization of allylic alcohols with rhodium and iridium complexes with ferrocene phosphine-thioether ligands","authors":"Ekaterina M. Titova ,&nbsp;S.M. Wahidur Rahaman ,&nbsp;Elena S. Shubina ,&nbsp;Rinaldo Poli ,&nbsp;Natalia V. Belkova ,&nbsp;Eric Manoury","doi":"10.1016/j.molcata.2016.08.014","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.014","url":null,"abstract":"<div><p>Complexes [M(P,SR)(diene)X] where (P,SR)<!--> <!-->=<!--> <!-->CpFe[1,2-C₅H₃(PPh₂)(CH₂SR)] (M<!--> <!-->=<!--> <!-->Ir, R<!--> <!-->=<!--> <!-->tBu or Bn diene<!--> <!-->=<!--> <!-->cod, X<!--> <!-->=<!--> <!-->Cl; M<!--> <!-->=<!--> <!-->Rh, diene<!--> <!-->=<!--> <!-->cod or nbd; X<!--> <!-->=<!--> <!-->BF₄ or Cl) were used as precatalysts for the redox isomerization of various allylic alcohols (<strong>7a–e</strong>) to the corresponding saturated ketones (<strong>8a–e</strong>) and or hydrogenation to the saturated alcohol (<strong>9a–e</strong>). In optimization studies using 1-phenyl-2-propen-1-ol (<strong>7a</strong>) in THF and in iPrOH/MeONa, the only observed product was the saturated alcohol 1-phenyl-1-propanol (<strong>9</strong>a) when working under a 30<!--> <!-->bar H₂ pressure, but activation for only 1<!--> <!-->min under H₂ pressure and then continuation under 1<!--> <!-->bar of H₂ or Ar led to increasing amounts of the allylic isomerization product propiophenone (<strong>8a</strong>). Continued reaction under H₂ converted (<strong>8a</strong>) into (<strong>9a</strong>). The Rh precatalysts were more active than the Ir analogues. For the rhodium precatalysts (<strong>3</strong>) and (<strong>4</strong>), the redox isomerization reaction could be carried out after precatalyst activation in iPrOH/MeONa under Ar at 82<!--> <!-->°C (without H₂) with complete conversion in 1<!--> <!-->h (1% catalyst loading). However, longer reaction times resulted in slow transfer hydrogenation of (<strong>8a</strong>) leading to (<strong>9a</strong>) with low enantiomeric excess. Extension of the H₂-free activation of the Rh precatalysts in iPrOH to other allylic alcohol substrates (<strong>7b–d</strong>) yielded the corresponding ketones with good to excellent yields and excellent chemoselectivities under appropriate conditions.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 376-380"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2879562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2","authors":"A. Simaioforidou,&nbsp;M. Papastergiou,&nbsp;A. Margellou,&nbsp;D. Petrakis,&nbsp;M. Louloudi","doi":"10.1016/j.molcata.2016.08.033","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.033","url":null,"abstract":"<div><p>Two types of heterogeneous catalytic materials, <strong>Mn^II-L₃imid@Cox</strong> and <strong>Mn^II-L₃imid@PCox</strong>, have been synthesized and compared by covalent grafting of a catalytically active [<strong>Mn^II-L₃imid]</strong> complex on the surface of an oxidized activated carbon (<strong>Cox)</strong> and an oxidized pyrolytic carbon from recycled-tire char (<strong>PCox)</strong>. Both hybrids are non-porous bearing graphitic layers intermixed with disordered sp²/sp³ carbon units. Raman spectra show that (I_D/I_G)_{activatedcarbon} <!-->&gt;<!--> <!-->(I_D/I_G)_{pyrolyticcarbon} revealing that oxidized activated carbon(<strong>Cox)</strong> is less graphitized than oxidized pyrolytic carbon (<strong>PCox)</strong>. The <strong>Mn^II-L₃imid@Cox</strong> and <strong>Mn^II-L₃imid@PCox</strong> catalysts were evaluated for alkene oxidation with H₂O₂ in the presence of CH₃COONH₄. Both showed high selectivity towards epoxides and comparing the achieved yields and TONs, they appear equivalent. However, <strong>Mn^II-L₃imid@PCox</strong> catalyst is kinetically faster than the <strong>Mn^II-L₃imid@Cox</strong> (accomplishing the catalytic runs in 1.5<!--> <!-->h <em>vs</em>. 5<!--> <!-->h). Thus, despite the similarity in TONs <strong>Mn^II-L₃imid@PCox</strong> achieved extremely higher TOFs <strong><em>vs</em>. Mn^II-L₃imid@Cox</strong>. Intriguingly, in terms of recyclability, <strong>Mn^II-L₃imid@Cox</strong> could be reused for a 2th run showing a ∼20% loss of its catalytic activity, while <strong>Mn^II-L₃imid@PCox</strong> practically no recyclable. This phenomenon is discussed in a mechanistic context; interlinking oxidative destruction of the Mn-complex with high TOFs for <strong>Mn^II-L₃imid@PCox</strong>, while the low-TOFs of <strong>Mn^II-L₃imid@Cox</strong> are preventive for the oxidative destruction of the Mn-complex.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 516-525"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1737687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanism of CuAAC reaction: In acetic acid and aprotic conditions","authors":"Cihan Özen,&nbsp;Nurcan Şenyurt Tüzün","doi":"10.1016/j.molcata.2016.11.010","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.010","url":null,"abstract":"<div><p>Protonation of copper-triazolide is a distinctive and final part in CuAAC reaction which has kinetic importance such that it can even affect the product distribution. In the context of this study, the protonation mechanism of copper-triazolide was investigated with quantum mechanical calculations to have a deeper understanding of the mechanism. In aprotic conditions where the alkyne is considered as proton donor, the key finding of DFT calculations performed in this study is that the activation energy barrier for the protonation step is greater than the cycloaddition step. In the absence of a strong proton donor the final protonation step is coupled with the alkyne deprotonation step in the catalytic cycle, which slows down the reaction. A conceivable pathway for acetic acid promoted CuAAC reaction on the basis of experimental and computational studies was also sought. With acetate as ligand, cycloaddition is a facile reaction and the energetics shows that it speeds up the cycloaddition step. Acetic acid in CuAAC reaction provides proton for the final protonation step in the catalytic cycle, decouples the protonation/deprotonation step by acting as a strong proton donor in the last step and facilitates protonation. The energetics presented herein are in accordance with the experimental proposals on rate-determining step in aprotic conditions and decreased reaction times obtained in the experiments in the presence of acetic acid.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 150-157"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2391733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure–activity comparison in palladium–N–heterocyclic carbene (NHC) catalyzed arene CH activation- functionalization","authors":"Moumita Mondal,&nbsp;Joyanta Choudhury","doi":"10.1016/j.molcata.2016.06.027","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.06.027","url":null,"abstract":"<div><p>A simple and efficient C<img>H activation catalyst was identified through a model structure-activity screening applied to a noncooperative, nonsymmetric bimetallic palladium(II)-N-heterocyclic carbene complex. Mechanistic studies based on kinetics and DOSY NMR spectroscopy provided the origin of the higher efficiency of the identified catalyst.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 451-457"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.06.027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2595831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols","authors":"Xingcui Guo ,&nbsp;Huihuan Dong ,&nbsp;Bin Li ,&nbsp;Linlin Dong ,&nbsp;Xindong Mu ,&nbsp;Xiufang Chen","doi":"10.1016/j.molcata.2016.11.003","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.003","url":null,"abstract":"<div><p>Different functional groups (i.e. <img>NH₂, <img>COOH, <img>OH and nitrogen-doping) modified CNTs (denoted as AMCN, CMCN, HMCN and NMCN, respectively) supported ruthenium catalysts (Ru/AMCN, Ru/CMCN, Ru/HMCN and Ru/NMCN) were prepared by incipient wetness impregnation method. They were fully characterized by XRD, TG, Raman, XPS, TPD and TEM to elucidate the relationship between the physical property and their catalytic performance. TEM results shown that Ru particles were well dispersed on the surface for all the samples with the size of 1.48–1.99<!--> <!-->nm. The effects of functional groups of carbon nanotubes (CNTs), nitrogen doping and base additive types on activity and selectivity of ethylene glycol (EG) and propylene glycol (1,2-PD) were investigated. In addition, the activity and final products distribution were much influenced by the properties of functional groups on CNTs and the type of metal cation of the base promoters, which probably participated in the reaction for accelerating a retro-aldol reaction for C<img>C cleavage. Among the catalysts, Ru supported on AMCN exhibited the best catalytic activities and glycols selectivities than on MCN, CMCN, HMCN and NMCN.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 79-87"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2878505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidation of aliphatic and aromatic CH bonds by t-BuOOH catalyzed by μ-nitrido diiron phthalocyanine","authors":"Evgeny V. Kudrik ,&nbsp;Alexander B. Sorokin","doi":"10.1016/j.molcata.2016.08.013","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.013","url":null,"abstract":"<div><p>Low temperature selective transformation of alkanes to useful products continues to be an important challenge in chemistry and industry. μ-Nitrido diiron phthalocyanines in combination with H₂O₂ have been recently identified as powerful oxidation catalysts for these challenging reactions due to the formation of ultra-high valent diiron oxo species PcFe(IV)μNFe(IV)<img>O(Pc⁺<img>). This very strong <em>two-electron oxidizing</em> species is generated from peroxo complex PcFe(IV)μNFe(III)<img>O<img>O<img>R(Pc) (R<img>H in the case of H₂O₂) via <em>heterolytic</em> O<img>O bond cleavage. Therein we show that the evolution of the peroxo diiron complex depends on the peroxide structure. Using ^tBuOOH we have demonstrated the formation of an <em>one-electron oxidizing</em> PcFe(IV)μNFe(IV)<img>O(Pc) and ^tBuO<img> radical via <em>homolytic</em> O<img>O cleavage of the peroxocomplex. The reactivity of the μ-nitrido diiron tetra-<em>t</em>-butylphthalocyanine − ^tBuOOH catalytic system was investigated in the oxidation of different C<img>H bonds in alkanes, olefins, aromatic and alkylaromatic compounds. The main products of cyclohexane oxidation were cyclohexanone and cyclohexanol whereas bicyclohexyl was formed in minor amounts even in the presence of O₂ and ^tBuOOH. Under optimal conditions, the turnover numbers of almost 5300 have been achieved.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 499-505"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2879561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Syntheses of bispyrazolyl monotriazolyl heteroscorpionate platinum(IV) complexes including an unusual Pt-CH2CH2-Pt bridge","authors":"Katherine D. Lavoie,&nbsp;Bryan E. Frauhiger,&nbsp;Peter S. White,&nbsp;Joseph L. Templeton","doi":"10.1016/j.molcata.2016.07.002","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.07.002","url":null,"abstract":"<div><p>Scorpionate ligands provide the benefit of hemilability while minimizing complete dissociation of the ligand. Previous investigations into Tp′PtL_nX_m complexes [Tp′<!--> <!-->=<!--> <!-->hydridotris(3,5-dimethylpyrazolyl)borate] revealed the importance of hemilability as the Tp′ ligand facilitates Pt(II/IV) interconversions. Here we discuss the synthesis and metalation of a series of asymmetric scorpionate ligands bearing two pyrazolyl rings and one triazolyl ring. In addition to utilizing triazole donor arms with differing substituents, we also compare octahedral structures of Pt(IV) complexes with P<!--> <!-->=<!--> <!-->O and C<img>H and B<img>H caps at the pole of the facial tridentate umbrella. Oxidation from Pt(II) to Pt(IV) with electrophilic reagents, simple acids and acid chlorides, leads to isomers in some cases, and the binding properties of the various donor arms dictate the stereochemistry of the products. Investigations into the reactivity of heteroscorpionate tridentate ligands bound to platinum(II) led to C<img>Cl activation reactions with methylene chloride and 1,2-dichloroethane. Isolation of a dinuclear platinum complex bridged by an ethylene unit produced an unusual proton NMR AA′XX′ pattern in the ¹H NMR spectrum due to chirality at each platinum center.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 474-489"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.07.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2171630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Zeolite Y encaged Ru(III) and Fe(III) complexes for oxidation of styrene, cyclohexene, limonene, and α-pinene: An eye-catching impact of H2SO4 on product selectivity","authors":"Dinesh R. Godhani,&nbsp;Haresh D. Nakum,&nbsp;Digvijaysinh K. Parmar,&nbsp;Jignasu P. Mehta,&nbsp;Nisheeth C. Desai","doi":"10.1016/j.molcata.2016.11.020","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.020","url":null,"abstract":"<div><p>A novel Ru(III) and Fe(III) complexes of ligands 1 and/or 2 {where 1<!--> <!-->=<!--> <!-->2,2′-((1E,1′E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene))diphenol and 2<!--> <!-->=<!--> <!-->2,2′-((1E,1′E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene)) bis(4-nitrophenol)} have been synthesized as ‘neat’ and zeolite Y encapsulated complexes. These catalysts are characterized by various analytical tools such as FTIR, UV–vis, elemental analysis, ICP-AES, molar conductivity, ¹H- and ¹³C NMR, TGA, SEM, AAS, BET, magnetic susceptibility and powder XRD to endorse the complex formation, absence of peripheral redundant ligands and complexes, conservation of zeolite Y morphology and crystallinity, and the encapsulation of complexes without devastation in the zeolite Y framework. Out of these synthesized catalysts, 5Y is found to be a potent candidate for styrene (Conv. 76.1%, TOF: 2130<!--> <!-->h⁻¹), cyclohexene (Conv. 84.4%, TOF: 2351<!--> <!-->h⁻¹), limonene (Conv. 81.6%, TOF: 2273<!--> <!-->h⁻¹), and α-pinene (Conv. 72.6%, TOF: 2023<!--> <!-->h⁻¹) oxidation with high selectivity of respective allylic products excluding the styrene oxidation, which undergoes epoxidation only. The addition of H₂SO₄ in an identical reaction catalyzed by 5Y <em>not only</em> surge the conversion up to 100% in a short time span with high TOF <em>but also</em> increase the selectivity of respective epoxidation products. This switchover in the selectivities could be credited to the presence of H₂SO₄ that facilitates the heterolytic <img>O<img>O<img> bond cleavage of metal hydroperoxide and stimulates the epoxidation over allylic oxidation. Furthermore, the results establish that the heterogeneous systems are effortlessly recovered and reused without ample drop in the activity and selectivity.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 223-237"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2171639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation of acetates catalyzed by boric acid and/or tungstophosphoric acid-modified zirconia obtained employing polyethylene glycols as pore-forming agents","authors":"Lilian Osiglio,&nbsp;Gabriel Sathicq,&nbsp;Luis Pizzio,&nbsp;Gustavo Romanelli,&nbsp;Mirta Blanco","doi":"10.1016/j.molcata.2016.11.004","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.004","url":null,"abstract":"<div><p>Zirconia modified with boric acid and/or tungstophosphoric acid calcined at 320<!--> <!-->°C were prepared, characterized and used as catalysts in the production of acetates from diverse alcohols and phenols. Polyethylene glycol (PEG) of different molecular weight (400, 2000, 6000<!--> <!-->Da) were added as low cost pore-forming agents during zirconia synthesis using zirconyl chloride as precursor and ammonium hydroxide as precipitating agent. The zirconias were impregnated with aqueous solutions of boric acid and/or tungstophosphoric acid (TPA). The borated zirconias, zirconias modified with TPA and zirconias doped with both boron and TPA were amorphous mesoporous materials with very strong acid sites, and specific surface areas S_BET of around 200, 100, and 150<!--> <!-->m²/g, respectively. The FT-IR spectra of borated zirconias exhibited the bands of boron species, while the zirconias modified with TPA presented the characteristic bands of tungstophosphate anion, and the zirconias doped with both boron and TPA showed a degradation of the TPA anion, confirmed by ³¹P MAS-NMR. The borated zirconias and the zirconias modified with TPA gave excellent selectivity and yield in the 2-phenylethanol esterification with acetic acid. The use of these materials allows obtaining higher or similar results than those reported in the literature. Zirconias doped with both boron and TPA gave lower values, due to the transformation of the [PW₁₂O₄₀]³⁻ Keggin anion in to the [P₂W₂₁O₇₁]⁶⁻ and [PW₁₁O₃₉]⁷⁻ species. The reactivity towards acetylation with acetic acid of different alcohols and phenols using the best catalyst was ordered according to: primary alcohols<!--> <!-->&gt;<!--> <!-->secondary alcohols<!--> <!-->&gt;<!--> <!-->phenols. The reactivity difference of the alcohols and phenols was correlated with the electronic density on the oxygen atom and steric effects.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 88-96"},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.004","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1737690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}