Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.09.028
Giovanna Bosica, Roderick Abdilla
Amberlyst A-21 supported CuI was found to be highly efficient novel heterogeneous catalyst for the three-component reaction between ketones, amines and alkynes, commonly called KA2-coupling. This inexpensive, easy-to-prepare, simple and recyclable catalyst has been employed in solventless conditions in the KA2 coupling reaction involving both primary and secondary amines, ketones and various alkynes. The secondary and tertiary propargylamine products were obtained in good to excellent results in moderate reaction times.
{"title":"The KA2 coupling reaction under green, solventless, heterogeneous catalysis","authors":"Giovanna Bosica, Roderick Abdilla","doi":"10.1016/j.molcata.2016.09.028","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.09.028","url":null,"abstract":"<div><p>Amberlyst A-21 supported CuI was found to be highly efficient novel heterogeneous catalyst for the three-component reaction between ketones, amines and alkynes, commonly called KA<sup>2</sup>-coupling. This inexpensive, easy-to-prepare, simple and recyclable catalyst has been employed in solventless conditions in the KA<sup>2</sup> coupling reaction involving both primary and secondary amines, ketones and various alkynes. The secondary and tertiary propargylamine products were obtained in good to excellent results in moderate reaction times.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.09.028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2595832","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.10.019
Akshai Kumar , Jason D. Hackenberg , Gao Zhuo , Andrew M. Steffens , Oleg Mironov , Robert J. Saxton , Alan S. Goldman
Conjugated dienes are desirable reagents for several important applications. We report that sterically uncrowded PCP-pincer iridium complexes, including precursors of (iPr4PCP)Ir and (Me2tBu2PCP)Ir, catalyze the transfer dehydrogenation of pentane, using high concentrations of t‐butylethylene (TBE) as hydrogen acceptor, to give high yields of 1,3-pentadiene (piperylene). Piperylene yields are ca. 100-fold greater than those obtained with the more widely used di(t‐butyl)phosphino substituted pincer iridium catalysts. This represents, to our knowledge, the first reported high-yield synthesis of dienes via the dehydrogenation of n-alkane using molecular catalysts. To our knowledge, this is the first reported high-yield synthesis of dienes achieved via the dehydrogenation of n-alkane using molecular catalysts.
{"title":"High yields of piperylene in the transfer dehydrogenation of pentane catalyzed by pincer-ligated iridium complexes","authors":"Akshai Kumar , Jason D. Hackenberg , Gao Zhuo , Andrew M. Steffens , Oleg Mironov , Robert J. Saxton , Alan S. Goldman","doi":"10.1016/j.molcata.2016.10.019","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.10.019","url":null,"abstract":"<div><p>Conjugated dienes are desirable reagents for several important applications. We report that sterically uncrowded PCP-pincer iridium complexes, including precursors of (<em><sup>i</sup></em><sup>Pr4</sup>PCP)Ir and (<sup>Me2<em>t</em>Bu2</sup>PCP)Ir, catalyze the transfer dehydrogenation of pentane, using high concentrations of <em>t</em>‐butylethylene (TBE) as hydrogen acceptor, to give high yields of 1,3-pentadiene (piperylene). Piperylene yields are ca. 100-fold greater than those obtained with the more widely used di(t‐butyl)phosphino substituted pincer iridium catalysts. This represents, to our knowledge, the first reported high-yield synthesis of dienes via the dehydrogenation of <em>n</em>-alkane using molecular catalysts. To our knowledge, this is the first reported high-yield synthesis of dienes achieved via the dehydrogenation of n-alkane using molecular catalysts.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.10.019","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2391728","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.08.037
Giselle C. Silva , Nakédia M.F. Carvalho , Adolfo Horn Jr. , Elizabeth R. Lachter , Octavio A.C. Antunes
In the present work, four mononuclear iron(III) complexes containing BMPA (BMPA = bis-(2-pyridylmethyl)amine) and derivative ligands, have been studied as catalyst in toluene oxidation, at 25 °C and 50 °C, using hydrogen peroxide as oxidant and acetonitrile as solvent. All catalysts were able to oxidize toluene with satisfactory yields, producing o-, m-, p-cresols, benzaldehyde and benzyl alcohol, as main products, and traces of 2-methylbenzoquinone and benzoic acid. The catalyst [Fe(BMPA)Cl3] presented the most promising results, reaching yields up to 30.2% at 50 °C after 24 h. Furthermore, [Fe(BMPA)Cl3] was applied in the oxidation of other aromatic compounds as benzene, ethylbenzene, cumene, n-propylbenzene, p-xylene and anisole. The reaction with H2O2 was monitored by electronic UV–vis spectroscopy in the presence and absence of toluene and its oxidation products, as well as by ESI-(+)-MS/Q-TOF mass spectrometry, in order to provide some information about the reaction mechanism.
本文研究了含BMPA (BMPA =双-(2-吡啶基甲基)胺)及其衍生物配体的四种单核铁(III)配合物在25℃和50℃下,以过氧化氢为氧化剂,乙腈为溶剂,作为甲苯氧化的催化剂。所有催化剂均能以满意的产率氧化甲苯,主要产物为邻甲酚、间甲酚、对甲酚、苯甲醛和苯甲醇,以及痕量的2-甲基苯醌和苯甲酸。催化剂[Fe(BMPA)Cl3]在50℃反应24 h后的产率可达30.2%。此外,[Fe(BMPA)Cl3]还应用于苯、乙苯、异丙苯、正丙苯、对二甲苯和苯甲醚等芳香族化合物的氧化。采用电子紫外-可见光谱法和ESI-(+)- ms /Q-TOF质谱法对反应过程进行了监测,对反应机理进行了初步探讨。
{"title":"Oxidation of aromatic compounds by hydrogen peroxide catalyzed by mononuclear iron(III) complexes","authors":"Giselle C. Silva , Nakédia M.F. Carvalho , Adolfo Horn Jr. , Elizabeth R. Lachter , Octavio A.C. Antunes","doi":"10.1016/j.molcata.2016.08.037","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.037","url":null,"abstract":"<div><p>In the present work, four mononuclear iron(III) complexes containing BMPA (BMPA<!--> <!-->=<!--> <!-->bis-(2-pyridylmethyl)amine) and derivative ligands, have been studied as catalyst in toluene oxidation, at 25<!--> <strong>°</strong>C and 50<!--> <strong>°</strong>C, using hydrogen peroxide as oxidant and acetonitrile as solvent. All catalysts were able to oxidize toluene with satisfactory yields, producing <em>o</em>-, <em>m</em>-, <em>p</em>-cresols, benzaldehyde and benzyl alcohol, as main products, and traces of 2-methylbenzoquinone and benzoic acid. The catalyst [Fe(BMPA)Cl<sub>3</sub>] presented the most promising results, reaching yields up to 30.2% at 50<!--> <strong>°</strong>C after 24<!--> <!-->h. Furthermore, [Fe(BMPA)Cl<sub>3</sub>] was applied in the oxidation of other aromatic compounds as benzene, ethylbenzene, cumene, <em>n</em>-propylbenzene, <em>p</em>-xylene and anisole. The reaction with H<sub>2</sub>O<sub>2</sub> was monitored by electronic UV–vis spectroscopy in the presence and absence of toluene and its oxidation products, as well as by ESI-(+)-MS/Q-TOF mass spectrometry, in order to provide some information about the reaction mechanism.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.037","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2391731","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.11.014
Abdel-Ghani Boudjahem , Mohammed M. Bettahar
The chemisorption and hydrogenating properties of Ni/SiO2 catalysts prepared by the hydrazine method then calcined at 400 °C with various times were investigated. Metal dispersion and activity in benzene hydrogenation increased with increasing calcination time whereas desorbed amounts of hydrogen significantly decreased. Dilution of a calcined sample by the support led to a sharp increase of both hydrogen storage by the support and catalytic activity. Metal dispersion and hydrogen storage capacity influenced the reaction mechanisms of hydrogenation of benzene which, therefore, is believed to occur on the metal phase or/and on the support by the hydrogen spillover mechanism. The metal active phase would be composed of an ensemble of metallic and oxidized nickel species.
{"title":"Effect of oxidative pre-treatment on hydrogen spillover for a Ni/SiO2 catalyst","authors":"Abdel-Ghani Boudjahem , Mohammed M. Bettahar","doi":"10.1016/j.molcata.2016.11.014","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.014","url":null,"abstract":"<div><p>The chemisorption and hydrogenating properties of Ni/SiO<sub>2</sub> catalysts prepared by the hydrazine method then calcined at 400<!--> <!-->°C with various times were investigated. Metal dispersion and activity in benzene hydrogenation increased with increasing calcination time whereas desorbed amounts of hydrogen significantly decreased. Dilution of a calcined sample by the support led to a sharp increase of both hydrogen storage by the support and catalytic activity. Metal dispersion and hydrogen storage capacity influenced the reaction mechanisms of hydrogenation of benzene which, therefore, is believed to occur on the metal phase or/and on the support by the hydrogen spillover mechanism. The metal active phase would be composed of an ensemble of metallic and oxidized nickel species.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2171637","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}
Catalytic systems RhCl3–KI–NaCl and RhCl3–Cu(OAcf)2–NaCl in aqueous perfluorinated carboxylic acids (CF3COOH, C3F7COOH) are effective in coupled oxidation of alkanes and carbon monoxide with dioxygen. In their presence, predominant is the outer-sphere oxidation of alkanes into respective esters (alcohols) with involvement of peroxo rhodium species as an oxidant (mechanism A). The process occurs partially by the inner-sphere mechanism B involving Rh–alkyl intermediates. Mechanism B is supported by (a) formation of alkyl chlorides, (b) synthesis of acetic acid in conversion of methane, and (c) positional selectivity in oxidation of propane.
{"title":"Homogeneous oxidation of alkanes: Role of rhodium–alkyl complexes","authors":"E.G. Chepaikin , A.P. Bezruchenko , G.N. Menchikova , А.Е. Gekhman","doi":"10.1016/j.molcata.2016.07.026","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.07.026","url":null,"abstract":"<div><p>Catalytic systems RhCl<sub>3</sub>–KI–NaCl and RhCl<sub>3</sub>–Cu(OAc<sub>f</sub>)<sub>2</sub>–NaCl in aqueous perfluorinated carboxylic acids (CF<sub>3</sub>COOH, C<sub>3</sub>F<sub>7</sub>COOH) are effective in coupled oxidation of alkanes and carbon monoxide with dioxygen. In their presence, predominant is the outer-sphere oxidation of alkanes into respective esters (alcohols) with involvement of peroxo rhodium species as an oxidant (mechanism <strong>A</strong>). The process occurs partially by the inner-sphere mechanism <strong>B</strong> involving Rh–alkyl intermediates. Mechanism B is supported by (a) formation of alkyl chlorides, (b) synthesis of acetic acid in conversion of methane, and (c) positional selectivity in oxidation of propane.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.07.026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2220003","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.11.002
Tae Hwan Lim , Su Bin Park , Ji Man Kim , Do Heui Kim
Ordered mesoporous MCo2O4 (M = Cu, Zn and Ni) spinel catalysts were synthesized via nano-replication method using mesoporous silica KIT-6 as the hard template. They were applied to methane combustion, in comparison with bulk MCo2O4 spinel catalysts prepared by co-precipitation method. A combined N2 adsorption-desorption, XRD and TEM results clearly confirm that mesoporous MCo2O4 (m-MCo2O4) spinel catalysts contain ordered mesostructure, resulting in the higher BET surface area and pore volume than bulk ones (b-MCo2O4). Moreover, the former catalysts demonstrate the better thermal stability as indicated by larger amount of MCo2O4 phase and smaller size of crystallite domain after calcination at 550 °C. Therefore, such excellent properties rationalize that the m-MCo2O4 spinel catalysts reveal higher catalytic activity for methane combustion than bulk counterparts. When it comes to the catalytic performance of the meso catalysts for methane combustion, the m-CuCo2O4 spinel catalyst has superior performance, which is related to the high normalized amount of Co3+ cations on the surface, as evidenced by XPS.
{"title":"Ordered mesoporous MCo2O4 (M = Cu, Zn and Ni) spinel catalysts with high catalytic performance for methane combustion","authors":"Tae Hwan Lim , Su Bin Park , Ji Man Kim , Do Heui Kim","doi":"10.1016/j.molcata.2016.11.002","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.002","url":null,"abstract":"<div><p>Ordered mesoporous MCo<sub>2</sub>O<sub>4</sub> (M<!--> <!-->=<!--> <!-->Cu, Zn and Ni) spinel catalysts were synthesized via nano-replication method using mesoporous silica KIT-6 as the hard template. They were applied to methane combustion, in comparison with bulk MCo<sub>2</sub>O<sub>4</sub> spinel catalysts prepared by co-precipitation method. A combined N<sub>2</sub> adsorption-desorption, XRD and TEM results clearly confirm that mesoporous MCo<sub>2</sub>O<sub>4</sub> (m-MCo<sub>2</sub>O<sub>4</sub>) spinel catalysts contain ordered mesostructure, resulting in the higher BET surface area and pore volume than bulk ones (b-MCo<sub>2</sub>O<sub>4</sub>). Moreover, the former catalysts demonstrate the better thermal stability as indicated by larger amount of MCo<sub>2</sub>O<sub>4</sub> phase and smaller size of crystallite domain after calcination at 550<!--> <!-->°C. Therefore, such excellent properties rationalize that the m-MCo<sub>2</sub>O<sub>4</sub> spinel catalysts reveal higher catalytic activity for methane combustion than bulk counterparts. When it comes to the catalytic performance of the meso catalysts for methane combustion, the m-CuCo<sub>2</sub>O<sub>4</sub> spinel catalyst has superior performance, which is related to the high normalized amount of Co<sup>3+</sup> cations on the surface, as evidenced by XPS.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2878504","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}
Zeolite catalyzed Friedel-Crafts acetylation of 2-methoxynaphthalene to produce 2-methoxy-6-acetylnaphthalene with high selectivity and conversion has been a challenging task, because the obtained compound is a key intermediate for an anti-inflammatory agent, Naproxen. However, no satisfactory results have been obtained with zeolite catalysts, and harmful solvents have been used to gain a high selectivity together with a high conversion. Here, we report the synthesis of 2-methoxy-6-acetylnaphthalene from 2-methoxynaphthalene with a high selectivity and a high conversion under an unprecedented simple reaction system; acetic anhydride as an acetylating agent, acetic acid as a solvent, and proton-type zeolite catalysts with low acidity. Among the examined zeolites, a proton-type H-MOR (SiO2/Al2O3 = 200) with a low acid content shows a conversion of 82% and an 86% selectivity for 2-methoxy-6-acetylnaphthalene. Further, detailed control experiments using H-MOR catalyst in acetic acid solvent were carried out to propose a plausible reaction mechanism.
{"title":"Zeolite catalyzed highly selective synthesis of 2-methoxy-6-acetylnaphthalene by Friedel-Crafts acylation of 2-methoxynaphthalene in acetic acid reaction media","authors":"Tomoyoshi Yamazaki, Makoto Makihara, Kenichi Komura","doi":"10.1016/j.molcata.2016.11.012","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.012","url":null,"abstract":"<div><p>Zeolite catalyzed Friedel-Crafts acetylation of 2-methoxynaphthalene to produce 2-methoxy-6-acetylnaphthalene with high selectivity and conversion has been a challenging task, because the obtained compound is a key intermediate for an anti-inflammatory agent, Naproxen. However, no satisfactory results have been obtained with zeolite catalysts, and harmful solvents have been used to gain a high selectivity together with a high conversion. Here, we report the synthesis of 2-methoxy-6-acetylnaphthalene from 2-methoxynaphthalene with a high selectivity and a high conversion under an unprecedented simple reaction system; acetic anhydride as an acetylating agent, acetic acid as a solvent, and proton-type zeolite catalysts with low acidity. Among the examined zeolites, a proton-type H-MOR (SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> <!-->=<!--> <!-->200) with a low acid content shows a conversion of 82% and an 86% selectivity for 2-methoxy-6-acetylnaphthalene. Further, detailed control experiments using H-MOR catalyst in acetic acid solvent were carried out to propose a plausible reaction mechanism.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2878507","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.10.010
Mainak Mitra , Hassan Nimir , David A. Hrovat , Albert A. Shteinman , Michael G. Richmond , Miquel Costas , Ebbe Nordlander
The oxidation reactions of alkanes with hydrogen peroxide and peracids (peracetic acid (PAA) and m-chloroperoxybenzoic acid (mCPBA)) catalysed by two Fe(II) complexes of pentadentate {N5}-donor ligands have been investigated. Kinetic isotope effect experiments and the use of other mechanistic probes have also been performed. While the total yields of oxidized products are similar regardless of oxidant (e.g. 30–39% for oxidation of cyclohexane), the observed alcohol/ketone ratios and kinetic isotope effects differ significantly with different oxidants. Catalytic reactions in H2O2 medium are consistent with the involvement of hydroxyl radicals in the CH bond cleavage step, and resultant low kinetic isotope effect values. On the other hand, catalytic reactions performed using peracid media indicate the involvement of an oxidant different from the hydroxyl radical. For these reactions, the kinetic isotope effect values are relatively high (within a range of 4.2–5.1) and the C3/C2 selectivity parameters in adamantane oxidation are greater than 11, thereby excluding the presence of hydroxyl radicals in the CH bond cleavage step. A low spin Fe(III)-OOH species has been detected in the H2O2-based catalytic system by UV/Vis, mass spectrometry and EPR spectroscopy, while an Fe(IV)-oxo species is postulated to be the active oxidant in the peracid-based catalytic systems. Computational studies on the CH oxidation mechanism reveal that while the hydroxyl radical is mainly responsible for the H-atom abstraction in the H2O2-based catalytic system, it is the Fe(IV)-oxo species that abstracts the H-atom from the substrate in the peracid-based catalytic systems, in agreement with the experimental observations.
{"title":"Catalytic C-H oxidations by nonheme mononuclear Fe(II) complexes of two pentadentate ligands: Evidence for an Fe(IV) oxo intermediate","authors":"Mainak Mitra , Hassan Nimir , David A. Hrovat , Albert A. Shteinman , Michael G. Richmond , Miquel Costas , Ebbe Nordlander","doi":"10.1016/j.molcata.2016.10.010","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.10.010","url":null,"abstract":"<div><p>The oxidation reactions of alkanes with hydrogen peroxide and peracids (peracetic acid (PAA) and <em>m</em>-chloroperoxybenzoic acid (mCPBA)) catalysed by two Fe(II) complexes of pentadentate {N<sub>5</sub>}-donor ligands have been investigated. Kinetic isotope effect experiments and the use of other mechanistic probes have also been performed. While the total yields of oxidized products are similar regardless of oxidant (e.g. 30–39% for oxidation of cyclohexane), the observed alcohol/ketone ratios and kinetic isotope effects differ significantly with different oxidants. Catalytic reactions in H<sub>2</sub>O<sub>2</sub> medium are consistent with the involvement of hydroxyl radicals in the C<img>H bond cleavage step, and resultant low kinetic isotope effect values. On the other hand, catalytic reactions performed using peracid media indicate the involvement of an oxidant different from the hydroxyl radical. For these reactions, the kinetic isotope effect values are relatively high (within a range of 4.2–5.1) and the C3/C2 selectivity parameters in adamantane oxidation are greater than 11, thereby excluding the presence of hydroxyl radicals in the C<img>H bond cleavage step. A low spin Fe(III)-OOH species has been detected in the H<sub>2</sub>O<sub>2</sub>-based catalytic system by UV/Vis, mass spectrometry and EPR spectroscopy, while an Fe(IV)-oxo species is postulated to be the active oxidant in the peracid-based catalytic systems. Computational studies on the C<img>H oxidation mechanism reveal that while the hydroxyl radical is mainly responsible for the H-atom abstraction in the H<sub>2</sub>O<sub>2</sub>-based catalytic system, it is the Fe(IV)-oxo species that abstracts the H-atom from the substrate in the peracid-based catalytic systems, in agreement with the experimental observations.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.10.010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2595829","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.11.001
Fang Wang , Tingting Wang , Junyu Lang, Yiguo Su, Xiaojing Wang
AgTaO3/AgBr heterojunction was constructed for visible light driven photocatalytic purpose in order to investigate the relevance of phase conversion, electronic structure and photocatalytic properties. The result indicated that AgBr grafted on AgTaO3 to form AgTaO3/AgBr heterojunction gave intense visible light absorption, which exhibits highly enhanced photocatalytic performance than their individual counterpart. Theoretical and experimental investigation showed that the matched electronic structure between AgTaO3 and AgBr induced an efficient transfer of photogenerated electrons from AgBr to AgTaO3, leading to efficient charge separation and the subsequent improved photocatalytic activity. Partial AgBr converted to AgBr/Ag during the photocatalytic process, leading to the construction of ternary AgTaO3/AgBr/Ag photocatalyst. Because of the surface plasmon resonance effect of Ag, the resulting AgTaO3/AgBr/Ag exhibited wide range absorption and improved charge separation efficiency, which showed high durability and superior photocatalytic activity toward methyl orange degradation. On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated electrons, O2−, and OH active species dominate the photodegradation of methyl orange.
{"title":"Improved photocatalytic activity and durability of AgTaO3/AgBr heterojunction: The relevance of phase and electronic structure","authors":"Fang Wang , Tingting Wang , Junyu Lang, Yiguo Su, Xiaojing Wang","doi":"10.1016/j.molcata.2016.11.001","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.001","url":null,"abstract":"<div><p>AgTaO<sub>3</sub>/AgBr heterojunction was constructed for visible light driven photocatalytic purpose in order to investigate the relevance of phase conversion, electronic structure and photocatalytic properties. The result indicated that AgBr grafted on AgTaO<sub>3</sub> to form AgTaO<sub>3</sub>/AgBr heterojunction gave intense visible light absorption, which exhibits highly enhanced photocatalytic performance than their individual counterpart. Theoretical and experimental investigation showed that the matched electronic structure between AgTaO<sub>3</sub> and AgBr induced an efficient transfer of photogenerated electrons from AgBr to AgTaO<sub>3</sub>, leading to efficient charge separation and the subsequent improved photocatalytic activity. Partial AgBr converted to AgBr/Ag during the photocatalytic process, leading to the construction of ternary AgTaO<sub>3</sub>/AgBr/Ag photocatalyst. Because of the surface plasmon resonance effect of Ag, the resulting AgTaO<sub>3</sub>/AgBr/Ag exhibited wide range absorption and improved charge separation efficiency, which showed high durability and superior photocatalytic activity toward methyl orange degradation. On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated electrons, O<sub>2</sub><sup>−</sup><img>, and OH<img> active species dominate the photodegradation of methyl orange.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660119","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}
Pub Date : 2017-01-01DOI: 10.1016/j.molcata.2016.08.020
Аlbert А. Shteinman
The quest of selective catalytic reactions for direct conversion of alkanes into valued products remains to be the most important task objective of modern chemistry and metal complex catalysis. Nowadays it is adopted that the formation of metal–alkyl intermediates (MR) is a necessary condition for activation and functionalization of alkanes on metal complexes but the mechanism of subsequent reactions of metal alkyls remain obscure, so that effective catalytic systems of this kind are still rare and uncommon. Although it is widely adopted that alkane σ-complexes (M·RH) most frequently are primary hydrocarbon intermediates in these processes, low profile in the literature is given to their reactivity and these are often considered simply just as some ‘collision complexes’. Nevertheless, theoretical and experimental studies provide more and more evidence that the СН bonds in such complexes may be markedly weakened and/or polarized, thus opening wide horizons for occurrence of subsequent direct homolytic or heterolytic reactions of alkanes. This review addresses the discussion of new routes for activation and oxygenation of saturated hydrocarbons, including those via alkane σ-complexes, without formation of metal–alkyl intermediates.
{"title":"Activation and selective oxy-functionalization of alkanes with metal complexes: Shilov reaction and some new aspects","authors":"Аlbert А. Shteinman","doi":"10.1016/j.molcata.2016.08.020","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.020","url":null,"abstract":"<div><p>The quest of selective catalytic reactions for direct conversion of alkanes into valued products remains to be the most important task objective of modern chemistry and metal complex catalysis. Nowadays it is adopted that the formation of metal–alkyl intermediates (M<img>R) is a necessary condition for activation and functionalization of alkanes on metal complexes but the mechanism of subsequent reactions of metal alkyls remain obscure, so that effective catalytic systems of this kind are still rare and uncommon. Although it is widely adopted that alkane σ-complexes (M·RH) most frequently are primary hydrocarbon intermediates in these processes, low profile in the literature is given to their reactivity and these are often considered simply just as some ‘collision complexes’. Nevertheless, theoretical and experimental studies provide more and more evidence that the С<img>Н bonds in such complexes may be markedly weakened and/or polarized, thus opening wide horizons for occurrence of subsequent direct homolytic or heterolytic reactions of alkanes. This review addresses the discussion of new routes for activation and oxygenation of saturated hydrocarbons, including those via alkane σ-complexes, without formation of metal–alkyl intermediates.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2393924","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}