- Role of Defects in Radiation Chemistry of Crystalline Organic Materials. 3. Geometrical and Electronic Structures of Alkene Radical Anion and Cation in Alkene/n-Alkane Mixed Crystals As Studied by ESR Spectroscopy
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An ESR study has been made in order to elucidate the electronic structures of alkene radical anion and cation, the former radical being first detected in the hexene/n-hexane mixed crystals irradiated at 4.2 K along with the cation.The present work extended to the hexene and butene isomers has resulted in evidence that both anions with vinylene and vinylidene groups have pyramidal structures with ?-character, which differ from the planar or twisted structures of corresponding cations.The proton hyperfine couplings of their anions were only about one-third as large asthose of the cations: A(two α-H) = 0.45, 0.1, -0.25 mT; a(two pairs of β-H) = 1.38 and 0.56 mT for the 3-hexene anion, and a(two α-H) = 1.3 mT and a(two pairs of β-H) = 4.6 and 2.9 mT for the cation.The differences in the geometrical structures and in the sizes of the proton couplings of the anion and cation radicals were discussed on the basis of a simple molecular orbital calculation.It has been found that the anion is stabilized by admixing 2s;C atomic orbitals (AO) with a lower core integral than 2p;C AO to the unpaired electron orbital and that the small β-proton couplings mainly originate from low extent of hyperconjugation due to a wide energy separation of C=C ?-antibonding and C-H pseudo-?-bonding orbitals.
- Matsuura, Kaoru,Muto, Hachizo,Nunome, Keichi
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- Nickle-Schiff base covalently grafted to UiO-66-NH2 as heterogeneous catalyst for ethylene oligomerization
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Metal organic frameworks (MOFs) UiO-66-NH2 had been modified by reaction of pyridine-2-carboxaldehyde with the amino groups to form a pyridineimine that act as ligand of metal Ni. The UiO-66-NH2 grafted pyridineimine nickel catalyst of post synthetic modification was assessed by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscope (SEM), inductively coupled plasma mass spectrometry (ICP-MS) and nitrogen adsorption–desorption, and the catalytic performance of the UiO-66-NH2 grafted pyridineimine nickel catalyst in ethylene oligomerization was investigated. The results showed that the catalyst structure, reaction temperature, Al/Ni molar ratio and reaction pressure had a significant effect on the catalytic activity and products selectivity. The catalytic activity of 3.76 × 105 g·(mol Ni·h)?1 and 75.94% selectivity of butene were obtained when the reaction temperature was 25 ℃, Al/Ni molar ratio was 1000 and reaction pressure was 1.2 MPa.
- Chen, Liduo,Jin, Rui,Li, Cuiqin,Mao, Guoliang,Tan, Jinyan,Wang, Jun,Zhang, Na
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- LIGANDS FOR PRODUCTION OF 1-HEXENE IN CHROMIUM ASSISTED ETHYLENE OLIGOMERIZATION PROCESS
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Catalyst compositions and processes for the oligomerization of ethylene to 1-hexene are described. The catalyst composition includes a triamino bisphospino (NPNPN) ligand system with specific phosphorous and nitrogen ligands. The terminal nitrogen atoms include linear alkyl hydrocarbons that differ in the number of carbon atoms by 3.
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Paragraph 0054-0056
(2022/01/12)
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- Phosphorus and nitrogen-doped palladium nanomaterials support on coral-like carbon materials as the catalyst for semi-hydrogenation of phenylacetylene and mechanism study
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In this work, two types of polyporous and coral-like materials (CN) with high specific surface area are prepared using sodium glutamate as a carrier. At the same time, a CN-supported phosphorus-nitrogen-doped palladium nanomaterial CN-P-Pd is synthesized and applied to the preparation of styrene by selective hydrogenation of phenylacetylene under mild conditions. As shown in the TEM images, Pd nanoparticles with a particle size of about 4.4 nm are uniformly dispersed on the surface of the carrier. The results of N2 adsorption–desorption reveal that the surface area of the prepared catalyst (CN-P-Pd) is 1307 m2g?1. In addition, the experimental exploration shows the intervention of P in carbon-nitrogen materials can contribute to improve the selectivity of the reaction, which can be attributed to the fact that P element can change the electron density of Pd. Meanwhile, it is found that the solvent not only affects the activity of catalyst, but also the selectivity of the reaction. Kinetic study shows the activation energy of the reaction is 4.5 kJ/mol. With the increase of the reaction temperature, the dissolution rate of hydrogen in the solvent gradually slows down, which inhibits the progress of the reduction reaction. Mechanistic studies demonstrate that the carbon-nitrogen materials have strong adsorption capacity for substrates, and also provide more adsorption sites for phenylacetylene. Additionally, the optimal catalyst (CN-P-Pd) also has high reaction activity to other alkynes and the conversion can reach at 95%. Moreover, the optimal catalyst can be reused several times without significant reduction in reaction activity.
- Ma, Lei,Jiang, Pengbo,Wang, Kaizhi,Lan, Kai,Huang, Xiaokang,Yang, Ming,Gong, Li,Jia, Qi,Mu, Xiao,Xiong, Yucong,Li, Rong
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- Precursor Nuclearity and Ligand Effects in Atomically-Dispersed Heterogeneous Iron Catalysts for Alkyne Semi-Hydrogenation
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Nanostructuring earth-abundant metals as single atoms or clusters of controlled size on suitable carriers opens new routes to develop high-performing heterogeneous catalysts, but resolving speciation trends remains challenging. Here, we investigate the potential of low-nuclearity iron catalysts in the continuous liquid-phase semi-hydrogenation of various alkynes. The activity depends on multiple factors, including the nuclearity and ligand sphere of the metal precursor and their evolution upon interaction with the mesoporous graphitic carbon nitride scaffold. Density functional theory predicts the favorable adsorption of the metal precursors on the scaffold without altering the nuclearity and preserving some ligands. Contrary to previous observations for palladium catalysts, single atoms of iron exhibit higher activity than larger clusters. Atomistic simulations suggest a central role of residual carbonyl species in permitting low-energy paths over these isolated metal centers.
- Faust Akl, Dario,Ruiz-Ferrando, Andrea,Fako, Edvin,Hauert, Roland,Safonova, Olga,Mitchell, Sharon,López, Núria,Pérez-Ramírez, Javier
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p. 3247 - 3256
(2021/05/31)
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- Seed-mediated Growth of Alloyed Ag-Pd Shells toward Alkyne Semi-hydrogenation Reactions under Mild Conditions?
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Ag@Ag-Pdx core-shell nanocomposites with various Ag/Pd ratio were deposited on Ag nanoplates using a seed growth method. When physically loaded on C3N4, Ag@Ag-Pd0.077/C3N4 with optimized Ag/Pd ratio could accomplish high catalytic performance for the semi-hydrogenation of phenylacetylene as well as other aliphatic (both terminal and internal alkynes) alkynes and phenylcycloalkynes containing functional groups (such as ester, hydroxyl, ethyl groups) under room temperature and 1 atm H2. The alloying and ensemble effects are used to interpret such catalytic performance.
- Zheng, Yuqin,Tan, Taixing,Wang, Cheng
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p. 3071 - 3078
(2021/09/13)
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- Ethylene oligomerization with 2-hydroxymethyl-5,6,7-trihydroquinolinyl-8-ylideneamine-Ni(II) chlorides
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A series of Ni complexes of the general formula [2-(MeOH)-8-{N(Ar)}C9H8N]NiCl2, where Ar = 2,6-Me2C6H3 in Ni1; 2,6-Et2C6H3 in Ni2; 2,6-i-Pr2C6H3 in Ni3; 2,4,6-Me3C6H2 in Ni4; 2,6-Et2-4-MeC6H2 in Ni5 and 2,4,6-t-Bu3C6H2 in Ni6 has been synthesized and characterized by elemental analysis and IR spectroscopy. On activation with MMAO or Et2AlCl, these complexes showed high activity in ethylene oligomerization, reaching 2.23 × 106 g·mol–1 (Ni) h–1 at 30 °C with the Al/Ni ratio of 5500 and 9.11 × 105 g·mol–1 (Ni) h–1 with the Al/Ni of 800, respectively. Moreover, the content of α-C4 indicated high selectivity exceeding 99% in the Ni/Et2AlCl system. Comparing with the previous report by our group, this work discloses higher activity, presumably due to the substituent at the 2-position within the ligand influencing the steric hindrance around the metal atom. Furthermore, it is worth noting that the branched alkenes have been observed (iso-C6: 35.3 – 57.2%) in the oligomerization products.
- Xu, Lei,Li, Jiaxin,Lin, Wenhua,Ma, Yanping,Hu, Xinquan,Flisak, Zygmunt,Sun, Wen-Hua
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- Faujasite silicalites for oxidative dehydrogenation of n-octane: Influence of alkali metals, gallium, and boron on catalyst activity
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The sol-gel method was used to synthesize faujasite type silicalites bearing gallium and boron in the framework. Barium and sodium were used as charge balancing cations since isomorphic substitution of Si4+ by Ga3+ or B3+ results in a negative excess charge of the framework. The successful synthesis of this type of silicalites (GaBaY-S, BBaY-S, GaBBaY-S(IE), GaNaY-S) was confirmed using powder-XRD. SEM analysis showed that the morphology of the catalysts with respect to particle size depended on the framework metals and the charge balancing cation used. Framework Ga containing catalysts showed smaller particle size compared to B containing catalysts. Sodium also yielded a smaller particle-sized catalyst compared to barium. The catalysts were tested in the continuous flow oxidative dehydrogenation (ODH) of n-octane, and the catalytic results showed dependence on the active metal reducibility and acid-base character of the catalysts. At iso-conversion of 8 ± 1 %, the least acidic BBaY-S gave the highest selectivity to octenes (40 %) and the lowest selectivity to COx (28 %), and the most acidic GaNaY-S showed the opposite results with octenes at 17 % and COx at 56 %. The catalysts (BaBY-S and GaBBaY-S(IE) with least total acidity had the greatest quantity of strong acid sites which were attributed to Lewis acid sites, confirmed by the pyridine IR analysis. The GaNaY-S, with the highest total acidity, had the least strong acid sites.
- Ndlela, Siyabonga S.,Friedrich, Holger B.,Cele, Mduduzi N.
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- Mild olefin formationviabio-inspired vitamin B12photocatalysis
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Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B12-dependent photoreceptor CarH, where photolysis of a cobalt-carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B12-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B12to be a powerful platform for developing mild olefin-forming reactions.
- Bam, Radha,Pollatos, Alexandros S.,Moser, Austin J.,West, Julian G.
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p. 1736 - 1744
(2021/02/22)
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- Rhodium-Catalyzed Regioselective Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes Using Formic Acid
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A rhodium-catalyzed hydroformylation of alkynes with formic acid was developed. The method provides α,β-unsaturated aldehydes in high yield and E-selectivity without the need to handle toxic CO gas.
- Fan, Chao,Hou, Jing,Chen, Yu-Jia,Ding, Kui-Ling,Zhou, Qi-Lin
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supporting information
p. 2074 - 2077
(2021/04/05)
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- Enantiopure 2,9-Dideuterodecane – Preparation and Proof of Enantiopurity
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(R,R)- and (S,S)-(2,9-2H2)-n-Decane were prepared regio- and stereospecifically in 25–26 % yield over five steps from commercially available enantiopure (R)- and (S)-propylene oxide, respectively. The synthetic procedure involved nucleophilic displacement of (R)- and (S)-4-toluenesulfonic acid 1-methyl-4-pentenyl ester with LiAlD4 to furnish the respective (5-2H)-1-hexenes. Subsequent olefin metathesis and reduction of the double bond furnished the title compounds. The optical purity of (R,R)- and (S,S)-(2,9-2H2)-n-decane could not be determined by chromatography or polarimetry. Therefore, (R,R)- and (R,S)-(5-2H)-3-hydroxy-2-hexanone were prepared from their respective hexenes by Wacker oxidation, followed by enantioselective α-hydroxylation. The enantiopurity could then be determined by NMR spectroscopy because the stereospecifically deuterated hydroxyketones showed separated signals for the subterminal carbon atom (C-5) in the 13C NMR spectrum.
- Christoffers, Jens,Eru?ar, Gülsera,Fsadni, Miriam H.,Golding, Bernard T.,Mitschke, Nico,Roberts, Amy R.,Sadeghi, Majid M.,Wilkes, Heinz
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p. 3854 - 3863
(2021/08/24)
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- Iridium(i) complexes bearing hemilabile coumarin-functionalised N-heterocyclic carbene ligands with application as alkyne hydrosilylation catalysts
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A set of iridium(i) complexes of formula IrCl(κC,η2-IRCouR′)(cod) or IrCl(κC, η2-BzIRCouR′)(cod) (cod = 1,5-cyclooctadiene; Cou = coumarin; I = imidazolin-2-carbene; BzI = benzimidazolin-2-carbene) have beeen prepared from the corresponding azolium salt and [Ir(μ-OMe)(cod)]2 in THF at room temperature. The crystalline structures of 4b and 5b show a distorted trigonal bipyramidal configuration in the solid state with a coordinated coumarin moiety. In contrast, an equilibrium between this pentacoordinated structure and the related square planar isomer is observed in solution as a consequence of the hemilability of the pyrone ring. Characterization of both species by NMR was achieved at the low and high temperature limits, respectively. In addition, the thermodynamic parameters of the equilibrium, ΔHR and ΔSR, were obtained by VT 1H NMR spectroscopy and fall in the range 22-33 kJ mol-1 and 72-113 J mol-1 K-1, respectively. Carbonylation of IrCl(κC,η2-BzITolCou7,8-Me2)(cod) resulted in the formation of a bis-CO derivative showing no hemilabile behaviour. The newly synthesised complexes efficiently catalyze the hydrosilylation of alkynes at room temperature with a preference for the β-(Z) vinylsilane isomer.
- ?zdemir, Ismail,Alici, Bülent,Castarlenas, Ricardo,Karata?, Mert Olgun,Pérez-Torrente, Jesús J.,Passarelli, Vincenzo
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p. 11206 - 11215
(2021/08/24)
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- Deoxygenation of Epoxides with Carbon Monoxide
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The use of carbon monoxide as a direct reducing agent for the deoxygenation of terminal and internal epoxides to the respective olefins is presented. This reaction is homogeneously catalyzed by a carbonyl pincer-iridium(I) complex in combination with a Lewis acid co-catalyst to achieve a pre-activation of the epoxide substrate, as well as the elimination of CO2 from a γ-2-iridabutyrolactone intermediate. Especially terminal alkyl epoxides react smoothly and without significant isomerization to the internal olefins under CO atmosphere in benzene or toluene at 80–120 °C. Detailed investigations reveal a substrate-dependent change in the mechanism for the epoxide C?O bond activation between an oxidative addition under retention of the configuration and an SN2 reaction that leads to an inversion of the configuration.
- Maulbetsch, Theo,Jürgens, Eva,Kunz, Doris
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p. 10634 - 10640
(2020/07/30)
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- An Annelated Mesoionic Carbene (MIC) Based Ru(II) Catalyst for Chemo- And Stereoselective Semihydrogenation of Internal and Terminal Alkynes
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The catalytic utility of [RuL1(CO)2I2] (1), containing an annelated π-conjugated imidazo-naphthyridine-based mesoionic carbene (MIC) ligand (L1), is evaluated for E-selective alkyne semihydrogenation. The precatalyst 1, in combination with 2 equiv of AgBArF, semihydrogenates a broad range of internal alkynes with molecular hydrogen (5 bar) in water. (E)-Alkenes are accessed in high yields, and a number of reducible functional groups are tolerated. A chelate MIC ligand and two cis carbonyls provide a well-defined platform at the Ru center for hydrogenation and isomerization. The loss of two iodides and the presence of two carbonyls render the Ru center electron deficient and thus the formation of metal vinylidenes with terminal alkynes is avoided. This is leveraged for the semihydrogenation of terminal alkynes by the same catalytic system in isopropyl alcohol. Reaction profile, isomerization, kinetic, and DFT studies reveal initial alkyne hydrogenation to a (Z)-alkene, which further isomerizes to an (E)-alkene via metal-catalyzed Z → E isomerization.
- Bera, Jitendra K.,Choudhury, Joyanta,Das, Shubhajit,Dutta, Indranil,Pati, Swapan K.,Saha, Sayantani,Yadav, Suman
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p. 3212 - 3223
(2020/10/02)
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- Accelerated Semihydrogenation of Alkynes over a Copper/Palladium/Titanium (IV) Oxide Photocatalyst Free from Poison and H2 Gas
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Selective hydrogenation of alkynes to alkenes (semihydrogenation) without the use of a poison and H2 is challenging because alkenes are easily hydrogenated to alkanes. In this study, a titanium (IV) oxide photocatalyst having Pd core-Cu shell nanoparticles (Pd@Cu/TiO2) was prepared by using the two-step photodeposition method, and Pd@Cu/TiO2 samples having various Cu contents were characterized by electron transmission microscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy. Thus-prepared Pd@Cu/TiO2 samples were used for photocatalytic hydrogenation of 4-octyne in alcohol and the catalytic properties were compared with those of Pd/TiO2 and Cu/TiO2. 4-Octyne was fully hydrogenated to octane over Pd/TiO2 at a high rate and 4-octyne was semihydrogenated to cis-4-octene over Cu/TiO2 at a low rate. Rapid semihydrogenation of 4-octyne was achieved over Pd(0.2 mol%)@Cu(1.0 mol%)/TiO2, indicating that the Pd core greatly activated the Cu shell that acted as reaction sites. A slight increase in the reaction temperature greatly increased the rate with a suppressed rate of H2 evolution as the side reaction. Changes in the reaction rates of the main and side reactions are discussed on the basis of results of kinetic studies. Reusability and expandability of Pd@Cu/TiO2 in semihydrogenation are also discussed.
- Imai, Shota,Nakanishi, Kousuke,Tanaka, Atsuhiro,Kominami, Hiroshi
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p. 1609 - 1616
(2020/02/15)
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- Constructing PtI?COF for semi-hydrogenation reactions of phenylacetylene
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The great efforts have been devoted to fabricate excellent hydrogenation catalysts owing to the broad applications in industrial fields. However, the preparation processes of traditional hydrogenation catalysts are often complicated. Herein, mono-valence PtI?COF was synthesized as a catalyst for semi-hydrogenation of phenylacetylene for the first time. The easily prepared SO3H-linked COF possesses a two-dimensional eclipsed layered-sheet structure, making its incorporation with metal ions feasible. The as-prepared PtI?COF composite exhibits excellent performance for semi-hydrogenation phenylacetylene with 93.5% conversion and 90.2% selectivity to styrene under mild reaction conditions (1 ?bar H2, 25 ?°C) within 20 ?min. It's worth noting that the turnover frequency (TOF) value reaches at 3965 h-1, which outperforms most of recently reported excellent Pt-based catalysts for this reaction.
- Li, Jian Hong,Yu, Zhi Wu,Li, Jian Qiang,Fan, Ya Ling,Gao, Zhi,Xiong, Jian Bo,Wang, Li,Tao, Yuan,Yang, Li Xiao,Xiao, Yu Xin,Luo, Feng
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- Transfer hydrogenation of alkynes into alkenes by ammonia borane over Pd-MOF catalysts
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Ammonia borane with both hydridic and protic hydrogens in its structure acted as an efficient transfer hydrogenation agent for selective transformation of alkynes into alkenes in non-protic solvents. Catalytic synergy between the μ3-OH groups of the UiO-66(Hf) MOF and Pd active sites in Pd/UiO-66(Hf) furnished an elusive >98% styrene selectivity and full phenylacetylene conversion at room temperature. Such performance is not achievable by a Pd + UiO-66(Hf) physical mixture or by a commercial Pd/C catalyst.
- Bakuru, Vasudeva Rao,Samanta, Debabrata,Maji, Tapas Kumar,Kalidindi, Suresh Babu
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supporting information
p. 5024 - 5028
(2020/05/08)
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- Nitrogen-fixing of ultrasmall Pd-based bimetallic nanoclusters on carbon supports
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Synthesis of supported Pd-based bimetallic catalysts is of great importance in the heterogeneous catalysis field owing to their optimal geometric and electronic effects. Downsizing active metals to ultrasmall nanocluster (2-reduction at 400–500 °C. Through the nitrogen-fixing strategy, we prepare 9 sub-2 nm Pd-based bimetallic nanocluster catalysts by conventional impregnation process. The prepared supported bimetallic Pd-Pb nanocluster catalyst exhibit a high turnover frequency of 1092 h?1 for the semihydrogenation of phenylacetylene under a mild condition (30 °C, 5 bar H2), along with a high selectivity of >93% to styrene, demonstrating the alloying and small-size effects in the bimetallic nanocluster catalysts.
- Chen, Ping,Liang, Hai-Wei,Shen, Shan-Cheng,Wang, Lei,Xu, Shi-Long,Yin, Peng,Zhang, Le-Le
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p. 297 - 304
(2020/07/03)
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- Accelerating Chemo- And Regioselective Hydrogenation of Alkynes over Bimetallic Nanoparticles in a Metal-Organic Framework
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Selective semihydrogenation of alkynes has been a long-term and significant target, yet it remains a great challenge. Herein, bimetallic nanoparticles in a metal-organic framework (MOF), i.e., CuPd&at;ZIF-8 composite, featuring a cubic CuPd core and a porous ZIF-8 shell, have been rationally fabricated for this end. Given the unique physicochemical properties, the Cu nanocubes can not only convert solar energy into heat to accelerate the reaction but also serve as the seed for in situ formation of Pd nanoparticles (NPs) on their external surface to regulate the chemoselectivity of Pd active sites. The additional growth of the MOF shell is helpful to stabilize the CuPd core and offer regioselectivity via the steric hindrance effect. Ammonia borane provides active hydrogen species to significantly boost the hydrogenation and ensure the high selectivity. As a result, the CuPd&at;MOF exhibits high efficiency, featuring a turnover frequency (TOF, 6799 min-1) of 5-105 times higher than that in previous reports, and high chemo- and regioselectivity toward the semihydrogenation of alkynes, in the presence of NH3BH3 as a hydrogen source, under visible-light irradiation at ambient temperature.
- Guan, Qiaoqiao,Jiang, Hai-Long,Li, Luyan,Lu, Junling,Yang, Qihao,Yang, Weijie,Yu, Shu-Hong
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p. 7753 - 7762
(2020/08/21)
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- Carrier-Induced Modification of Palladium Nanoparticles on Porous Boron Nitride for Alkyne Semi-Hydrogenation
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Chemical modifiers enhance the efficiency of metal catalysts in numerous applications, but their introduction often involves toxic or expensive precursors and complicates the synthesis. Here, we show that a porous boron nitride carrier can directly modify supported palladium nanoparticles, originating unparalleled performance in the continuous semi-hydrogenation of alkynes. Analysis of the impact of various structural parameters reveals that using a defective high surface area boron nitride and ensuring a palladium particle size of 4–5 nm is critical for maximizing the specific rate. The combined experimental and theoretical analyses point towards boron incorporation from defects in the support to the palladium subsurface, creating the desired isolated ensembles determining the selectivity. This practical approach highlights the unexplored potential of using tailored carriers for catalyst design.
- Büchele, Simon,Chen, Zupeng,Fako, Edvin,Hauert, Roland,Krumeich, Frank,López, Núria,Mitchell, Sharon,Pérez-Ramírez, Javier,Safonova, Olga V.
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supporting information
p. 19639 - 19644
(2020/08/19)
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- Mono-cyclopentadienyl tetravalent transition metal complex containing neutral benzyl heteroatom ligand side arm and application thereof
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The invention relates to the field of ethylene oligomerization catalysis, and particularly discloses a mono-cyclopentadienyl tetravalent transition metal complex containing a neutral benzyl heteroatomligand side arm and application thereof. The mono-cyclo
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Paragraph 0110-0112
(2020/09/16)
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- Silver(I) and Nickel(II) Complexes with Oxygen- or Nitrogen-Functionalized NHC Ditopic Ligands and Catalytic Ethylene Oligomerization
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Potentially bidentate ditopic ligands containing a N-heterocyclic carbene (NHC) donor associated with an ether or an amine have been prepared and coordinated to NiII centers. The influence of the length of the alkyl chain, –(CH2)2– or –(CH2)3– connecting the ether or the amine group to the heterocycle was examined. In the analogous AgI complexes [Ag{Im(Dipp)(C3OMe)-κ1CNHC}2]Cl (8), 9 and 10, in the neutral NiII complexes with a C3 spacer trans-[NiCl2{Im(Dipp)(C3OMe)-κ1CNHC}2] (5a), 6, and 7, and in the cationic cis-[Ni{Im(Dipp)(C3OMe)-κ1CNHC}2(NCMe)2](PF6)2 (15) and cis-[Ni{Im(Mes)(C3OMe)-κ1CNHC}2(NCMe)2](PF6)2 (16), the ligand is monodentate. [(ImH)(Dipp)(C3OMe)][NiX3{Im(Dipp)(C3OMe)-κ1CNHC}] (14a, X = Cl) and (14b, X = Br) are rare examples of complexes of the type [NiX3(NHC)]–. For comparison, [NiBr2{(Im)(Dipp)(C2NMe2)-κ2,CNHC,Namine}] (24) and [NiBr2{(Im)(Dipp)(C3NMe2)-κ2,CNHC,Namine}] (25) contain a six- or a seven-membered κ2CNHC,Namine chelate, respectively. Various NiII complexes were evaluated as precatalysts for ethylene oligomerization. The structures of the carbene (Dipp)(C3OMe)imidazole-ylidene (4) and of the complexes 5a, 7, 8, [(ImH)(Dipp)(C3OMe)]2[NiCl4] (11a), [(ImH)(Dipp)(C3OMe)]2[NiBr4] (11b), [(ImH)(Me)(C3OMe)]2[NiCl4] (13), 14b, 16·NCMe, [Im(H){C(Me)(=NDipp)}(C3OMe)]2 [NiCl4] (18), [AgCl{Im[C(Me)=NDipp](C3OMe)}-κ1CNHC] (19), [AgCl{Im(Dipp)(C3NMe2)-κ1CNHC}] (23), 24, 25 and trans-[NiCl2{Im(Dipp){CH2CH2C(O)OEt}}2] were analyzed by X-ray diffraction.
- Ren, Xiaoyu,Wesolek, Marcel,Bailly, Corinne,Karmazin, Lydia,Braunstein, Pierre
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p. 1073 - 1087
(2020/01/02)
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- 2-(: N, N -Diethylaminomethyl)-6,7-trihydroquinolinyl-8-ylideneamine-Ni(ii) chlorides: Application in ethylene dimerization and trimerization
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A series of Ni(ii) complexes with the general formula [2-((NEt2)Me)-8-{N(Ar)}C9H8N]NiCl2, where Ar = 2,6-Me2C6H3 in Ni1, 2,6-Et2C6H3 in Ni2, 2,6-i-Pr2C6H3 in Ni3, 2,4,6-Me3C6H2 in Ni4, 2,6-Et2-4-MeC6H2 in Ni5, and 2,4,6-t-Bu3C6H2 in Ni6, has been prepared using a one-pot reaction of 2-(N,N-diethylaminomethyl)-6,7-dihydroquinolin-8(5H)-one with the corresponding aniline and nickel dichloride hexahydrate. The resultant complexes were characterized using elemental analysis and FT-IR spectroscopy, while the mononuclear Ni1 and Ni3 were also the subject of single-crystal X-ray diffraction study. On activation with MMAO, the complexes Ni1-Ni6 displayed good activity in ethylene oligomerization, forming hexenes (ca. 48% 1-hexene) as the major products and exhibiting thermal stability up to 50 °C under 10 atm C2H4. When MAO was applied as the cocatalyst, lower activity was observed, but the catalyst showed higher selectivity toward ethylene dimerization. It is also worth noticing that an induction period was observed as the Ni/MAO catalysts reached their peak activity after 30 min. This journal is
- Li, Jiaxin,Ma, Yanping,Hu, Xinquan,Flisak, Zygmunt,Tongling, Liang,Sun, Wen-Hua
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p. 17047 - 17052
(2020/10/27)
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- Method for eliminating hydrogen chloride by catalytic cracking of chloralkane
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The invention discloses a method for eliminating hydrogen chloride by catalytic cracking of chloralkane, comprising the following steps of: carrying out a cracking reaction on chloralkane under the action of a biomass-based nitrogen-doped carbon catalyst to eliminate hydrogen chloride so as to prepare corresponding olefin, wherein the biomass-based nitrogen-doped carbon catalyst is prepared by carbonizing biomass or a mixture of biomass and a nitrogen source at 400-1000 DEG C, and the biomass is selected from at least one of bamboo processing leftovers, wood processing leftovers, plant straws,plant leaves, cereals, beans, cereal processing leftovers, bean processing leftovers and livestock manure. The method disclosed by the invention has the advantages of simple preparation process, easily available raw materials, low cost, strong process controllability, easiness in large-scale production, high catalytic cracking conversion rate of the chloralkane, high product selectivity, low energy consumption and the like.
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Paragraph 0148-0153
(2020/08/06)
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- Method for Oligomerizing Ethylene
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The present invention relates to an oligomerization method of ethylene using a reactor equipped with a condenser, wherein the method comprises a step of pre-mixing a raw material composition at a low temperature, introducing the composition into the reactor, and inducing an ethylene oligomerization reaction at a low reaction pressure. According to the method of the present invention, it is possible to prepare an oligomer having excellent reaction activity and product selectivity, and even if the oligomerization reaction proceeds at a low pressure condition, energy consumption is reduced compared to a conventional heat removal method.COPYRIGHT KIPO 2020
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Paragraph 0054-0060
(2020/09/04)
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- Phospholane-Based Ligands for Chromium-Catalyzed Ethylene Tri- And Tetramerization
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Chromium complexes with bis(phospholane) ligands were synthesized and evaluated for ethylene tetramerization in a high-throughput reactor. Three ligand parameters - the phospholane substituent, the ligand backbone, and the type of phosphine (cyclic vs acyclic) - were investigated. The size of the phospholane substituent was found to impact the selectivity of the resulting catalysts, with smaller substituents leading to the production of larger proportions of 1-octene. Changing the ligand backbone from 1,2-phenylene to ethylene did not impact catalysis, but the use of acyclic phosphines in place of the cyclic phospholanes had a detrimental effect on catalytic activity. Selected phospholane-chromium complexes were evaluated in a 300 mL Parr reactor at 70 °C and 700 psi of ethylene pressure, and the ethylene oligomerization performance was consistent with that observed in the smaller, high-throughput reactor. MeDuPhos-CrCl3(THF) (MeDuPhos = 1,2-bis(2,5-dimethylphospholano)benzene; THF = tetrahydrofuran) gave activity and selectivity for 1-octene (54.8 wt %) similar to the state-of-the-art i-PrPNP-CrCl3(THF) (64.0 wt %) (PNP = bis(diphenylphosphino)amine), while EtDuPhos-CrCl3(THF) (EtDuPhos = 1,2-bis(2,5-diethylphospholano)benzene) exhibited even higher activity, with catalyst selectivity shifted toward 1-hexene production (90 wt %). These results are surprising, given the prevalence of the aryl phosphine motif in ligands used in ethylene oligomerization catalysts and the inferior performance of previously reported catalysts with alkyl phosphine-containing ligands.
- Boelter, Scott D.,Davies, Dan R.,Klosin, Jerzy,Margl, Peter,Milbrandt, Kara A.,Mort, Darrek,Rosen, Mari S.,Vanchura, Britt A.,Wilson, David R.,Wiltzius, Molly
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supporting information
(2020/02/27)
-
- Ethylene Tetramerisation: A Structure-Selectivity Correlation
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The effect of ethylene tetramerisation ligand structures on 1-octene selectivity is well studied. However, by-product formation is less understood. In this work, a range of PNP ligand structures are correlated with the full product selectivity and with catalyst activity. As steric bulk on the N-substituent increases, the product selectivity shifts from >10 % to 3% of both C6 cyclics and C16+ by-products. 1-Octene peaks at ca. 70%. Thereafter, only 1-hexene increases. Similar selectivity changes were observed for ortho-Ph-substituted PNP ligands. The C10-14 selectivity was less affected by the ligand structure. The ligand effect on the changes in selectivity is explained mechanistically. Lastly, an increase in ligand steric bulk was found to improve catalyst activity and reduce polymer formation by an order of magnitude. It is proposed that steric bulk promotes formation of cationic catalytic species which are responsible for selective ethylene oligomerisation.
- Makume, Boitumelo F.,Holzapfel, Cedric W.,Maumela, Munaka C.,Willemse, J. Alexander,van den Berg, Jan A.
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p. 2308 - 2315
(2020/11/03)
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- PROCESS
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A process for dehydrating C2+ alcohols to ether products in the presence of a catalyst and promoter, wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a medium pore zeolite having a 3-dimensional framework structure, and the promoter is one or more organic carbonyl compounds or derivatives thereof, and wherein and the molar ratio of promoter to C2+ alcohols is maintained at less than 1.
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Page/Page column 31-32
(2020/09/08)
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- A Cp-based Molybdenum Catalyst for the Deoxydehydration of Biomass-derived Diols
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Dioxo-molybdenum complexes have been reported as catalysts for the deoxydehydration (DODH) of diols and polyols. Here, we report on the DODH of diols using [Cp*MoO2]2O as catalyst (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl). The DODH reaction was optimized using 2 mol % of [Cp*MoO2]2O, 1.1 equiv. of PPh3 as reductant, and anisole as solvent. Aliphatic vicinal diols are converted to the corresponding olefins by [Cp*MoO2]2O in up to 65 % yield (representing over 30 turnovers per catalyst) and 91 % olefin selectivity, which rivals the performance of other Mo-based DODH catalysts. Remarkably, cis-1,2-cyclohexanediol, which is known as quite a challenging substrate for DODH catalysis, is converted to 30 % of 1-cyclohexene under optimized reaction conditions. Overall, the mass balances (up to 79 %) and TONs per Mo achievable with [Cp*MoO2]2O are amongst the highest reported for molecular Mo-based DODH catalysts. A number of experiments aimed at providing insight in the reaction mechanism of [Cp*MoO2]2O have led to the proposal of a catalytic pathway in which the [Cp*MoO2]2O catalyst reacts with the diol substrate to form a putative nonsymmetric dimeric diolate species, which is reduced in the next step at only one of its Mo-centers before extrusion of the olefin product.
- Li, Jing,Lutz, Martin,Klein Gebbink, Robertus J. M.
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p. 6356 - 6365
(2020/11/30)
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- Deoxygenation of heptanoic acid to hexene over cobalt-based catalysts: A model study for α-olefin production from renewable fatty acid
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Deoxygenation of heptanoic acid, a model compound, over bimetallic cobalt (Co-Pt, Co-Au, Co-Pd, Co-Ru) supported silica catalysts, was examined for α-olefin production. The catalysts were prepared by conventional impregnation of the metal precursors on silica and characterized by XRF, TEM, H2-TPR, acetic acid-TPD, and XANES. Catalytic testing was performed in a fixed-bed flow reactor under atmospheric H2 pressure. Monometallic cobalt catalysts yielded mainly 1-hexene, but rapid deactivation was observed. Incorporation of 0.5percentwt secondary metal, particularly Pt, increases activity and stability under H2. A relatively higher olefin/paraffin ratio can be obtained from the reaction over 5percentCo+0.5percentPt/SiO2 when compared to that with higher Pt loading. The co-impregnation method offers Co-Pt catalysts with stability higher than that prepared by the sequential impregnation method. Over cobalt-based catalysts, the deoxygenation is proposed to proceed via reduction of heptanoic acid to heptanal that is an intermediate for decarbonylation to hexene; while other side reactions are suppressed.
- Choojun, Kittisak,Phichitsurathaworn, Ploynisa,Poo-arporn, Yingyot,Sooknoi, Tawan
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-
- Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
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The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand.
- Greaves, Megan E.,Lloyd-Jones, Guy C.,Maseras, Feliu,Nelson, David J.,Ronson, Thomas O.,Sproules, Stephen
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p. 10717 - 10725
(2020/11/09)
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- Ethylene oligomerization promoted by nickel-based catalysts with silicon-bridged diphosphine amine ligands
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A series of nickel complexes [Ni(L1)Br2] (C1), [Ni(L2)Br2] (C2) and [Ni(L3)Br2] (C3) (L1 = N-isopropyl-N-(((diphenylphosphanyl)methyl)dimethylsilyl)-1,1-diphenylphosphanamine, L2 = N-cyclopentyl-N-(((diphenylphosphanyl)methyl)dimethylsilyl)-1,1-diphenylphosphanamine, L3 = N-(2,6-diisopropylphenyl)-N-(((diphenylphosphanyl)methyl)dimethylsilyl)-1,1-diphenylphosphanamine) were synthesized and characterized by elemental analysis, mass spectrometry, spectroscopy and single-crystal X-ray diffraction. L1, L2 and L3 each act as bidentate ligands. Upon activation with ethylaluminum dichloride, these complexes produce efficient catalytic systems for selective dimerization of ethylene to 1-butene, with catalytic activities of 3.45 × 107?g/(molNi·h) and 95.6% butene selectivity containing 87.6% 1-butene fraction.
- Wei, Wei,Yu, Buwei,Alam, Fakhre,Huang, Yongwang,Cheng, Shaoling,Jiang, Tao
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p. 125 - 133
(2018/10/02)
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- Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
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Modification of transition metals with p-block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi-hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi-hydrogenation of 1-hexyne and 2-methyl-3-butyn-2-ol shows that the phosphides present higher rate and selectivity than unmodified nickel catalysts. While no activity and selectivity differences are displayed in the semi-hydrogenation of 1-hexyne over Ni2P and Ni5P4, in the case of 2-methyl-3-butyn-2-ol a higher rate and lower selectivity to 2-methyl-3-buten-2-ol are observed over Ni2P. Density functional theory reveals that the hydroxyl group facilitates the reaction, but also increases the barrier for product desorption. Detailed analyses of the ensemble show the potential of phosphorus to create spatially-isolated nickel trimers that surpass the performance of unmodified nickel, but also its limited ability to modulate the electronic properties and related binding energies of organic intermediates, which is key to preventing undesired side reactions.
- Albani, Davide,Karajovic, Konstantin,Tata, Bharath,Li, Qiang,Mitchell, Sharon,López, Núria,Pérez-Ramírez, Javier
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p. 457 - 464
(2018/11/27)
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- Dendrimer-Encapsulated Pd Nanoparticles, Immobilized in Silica Pores, as Catalysts for Selective Hydrogenation of Unsaturated Compounds
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Heterogeneous Pd-containing nanocatalysts, based on poly (propylene imine) dendrimers immobilized in silica pores and networks, obtained by co-hydrolysis in situ, have been synthesized and examined in the hydrogenation of various unsaturated compounds. The catalyst activity and selectivity were found to strongly depend on the carrier structure as well as on the substrate electron and geometric features. Thus, mesoporous catalyst, synthesized in presence of both polymeric template and tetraethoxysilane, revealed the maximum activity in the hydrogenation of various styrenes, including bulky and rigid stilbene and its isomers, reaching TOF values of about 230000 h?1. Other mesoporous catalyst, synthesized in the presence of polymeric template, but without addition of Si(OEt)4, provided the trans-cyclooctene formation with the selectivity of 90–95 %, appearing as similar to homogeneous dendrimer-based catalysts. Microporous catalyst, obtained only on the presence of Si(OEt)4, while dendrimer molecules acting as both anchored ligands and template, demonstrated the maximum activity in the hydrogenation of terminal linear alkynes and conjugated dienes, reaching TOF values up to 400000 h?1. Herein the total selectivity on alkene in the case of terminal alkynes and conjugated dienes reached 95–99 % even at hydrogen pressure of 30 atm. The catalysts synthesized can be easily isolated from reaction products and recycled without significant loss of activity.
- Karakanov, Edward A.,Zolotukhina, Anna V.,Ivanov, Andrey O.,Maximov, Anton L.
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p. 358 - 381
(2019/04/04)
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- Ultralow-content palladium dispersed in covalent organic framework for highly efficient and selective semihydrogenation of alkynes
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Developing noble-metal-based catalysts with ultralow loading to achieve excellent performance for selective hydrogenation of alkynes under mild reaction conditions is highly desirable but still faces huge challenges. To this end, a SO3H-anchored covalent organic framework (COF-SO3H) as the support was deliberately designed, and then ultralow-content Pd (0.38 wt %) was loaded by a wet-chemistry immersion dispersion method. The resulting Pd0.38/COF-SO3H composite exhibits outstanding performance for the selective hydrogenation of phenylacetylene with 97.06% conversion and 93.15% selectivity to styrene under mild reaction conditions (1 bar of H2, 25 °C). Noticeably, the turnover frequency value reaches as high as 3888 h-1, which outperforms most of reported catalysts for such use. Moreover, such a catalyst also exhibits excellent activity for a series of other alkynes and high stability without obvious loss of catalytic performance after five consecutive cycles.
- Li, Jian Hong,Yu, Zhi Wu,Gao, Zhi,Li, Jian Qiang,Tao, Yuan,Xiao, Yu Xin,Yin, Wen Hui,Fan, Ya Ling,Jiang, Chao,Sun, Li Jun,Luo, Feng
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supporting information
p. 10829 - 10836
(2019/08/22)
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- Perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene
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A catalyst system comprising an N2-phosphinylamidine chromium salt complex having Structure PFHNPACr I: wherein Rf1, Rf2, Rf4, and Rf5 are independently selected from a perfluorohydrocarbyl group; and CrXp is a chromium salt; X is a monoanion, and p is an integer from 2 to 6. A process comprising a) contacting i) ethylene, ii) a catalyst system comprising an N2-phosphinylamidine chromium salt complex having Structure PFHNPACr I: wherein each Rf1, Rf2, Rf4, and Rf5 are independently selected from a perfluorohydrocarbyl group and CrXp is a chromium salt; X is a monoanion and p is an integer from 2 to 6, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.
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Page/Page column 40-44
(2019/02/07)
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- Nickel(II) complexes with tripodal NNN ligands as homogenous and supported catalysts for ethylene oligomerization
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Four new coordination compounds of nickel (II) with derivatives of N,N-bis(pyrazol-1-ylmethyl)propylamine were synthesized; their composition and structure were confirmed with IR-spectroscopy and elemental analysis. The structures of products 13 and 15 were unambiguously established in an X-ray diffraction study. Compounds 13 and 15 crystallize in the orthorhombic space groups Pna21 and P212121 correspondingly and represent a monomeric octahedral nickel complexes, that are typical for tridentate scorpion-type ligands. New method for immobilization of nickel complexes with derivatives of N,N-bis(pyrazol-1-ylmethyl)propylamine on silica gel modified with aminopropyl groups was proposed. The EXAFS/XANES analysis indicated that Ni atom in the supported complexes adopt almost octahedral geometry, being partly surrounded by nitrogen atoms from organic ligand and partly grafted to silica surface through silanol groups, with Br? in outer coordination sphere. Both the original and the supported complexes, when activated with Et2AlCl or Et3Al2Cl3, catalyze ethylene oligomerization with the predominant formation of butene isomers. Generally, the immobilized complexes show higher activity and better selectivity towards 1-butene formation.
- Tuskaev, Vladislav A.,Zubkevich, Sergei V.,Saracheno, Daniele,Gagieva, Svetlana Ch.,Dorovatovskii, Pavel V.,Kononova, Elena G.,Khrustalev, Victor N.,Zarubin, Dmitry N.,Bulychev, Boris M.,Kissin, Yury V.
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-
- Chromium complexes based on thiophene–imine ligands for ethylene oligomerization
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A new set of Cr(III) complexes, {L}CrCl3(THF), based on thiophene–imine (2a, L?=?PhOC6H4(N═CH)-2-SC4H3; 2b, L?=?PhOC2H4(N═CH)-2-SC4H3; 2c, L?=?Ph(NH)C2H4(N═CH)-2-SC4H3; 2d, L?=?PhOC6H4(N═CH)-2-SC4H2-5-Ph; 2e, L?=?Ph(NH)C2H4(N═CH)-2-SC4H2-5-Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α-olefins with turnover frequencies in the range 9500–93?500?(mol ethylene)?(mol Cr)?1?h?1, and producing mostly oligomers (95.0–99.3?wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2?wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined.
- Ferreira, Jorge,Zilz, Raquel,Boeira, Igor S.,da Silva, Sabrina M.,Casagrande, Adriana C.A.,Casagrande, Osvaldo L.
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- Activated Niobium and Tantalum Imido Complexes: From Tuneable Polymerization to Selective Ethylene Dimerization Systems
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The niobium and tantalum imido complexes [CpMCl2(NDipp)], [MCl3(NR)(dme)] (R=tBu, Ph, 2,6-iPr2C6H3 (Dipp), and Mes), and [TaCl3(NDipp)(tmeda)] were tested in combination with EtAlCl2 for the dimerization of ethylene. The niobium systems afforded dimers or polymers, depending on the nature of the imido ligand, with overall productivities in the range 720 to 13,720 (mol C2H4)(mol Nb)?1. The nature of the polyethylene produced (LDPE or HDPE) depended on the imido ligand and the niobium concentration at which catalysis was run. In contrast, the tantalum/dme systems all mediated ethylene dimerization with productivities of up to 4,503 (mol C2H4)(mol Ta)?1, with overall selectivities to butenes of between 73–81 wt %; selectivity within the dimer fraction to 1-butene was in the range 72 to 100 %. The productivity of [TaCl3(NDipp)(tmeda)] was six times higher than that of its dme-bearing counterpart, but at the cost of selectivity to 1-butene. For the tantalum imido-mediated ethylene dimerization the composition of the product slate formed is indicative of a metallacyclic mechanism being operative.
- Messinis, Antonis M.,Batsanov, Andrei S.,Howard, Judith A. K.,Hanton, Martin J.,Dyer, Philip W.
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p. 1756 - 1764
(2019/02/26)
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- (Arylimido)niobium(V) Complexes Containing 2-Pyridylmethylanilido Ligand as Catalyst Precursors for Ethylene Dimerization That Proceeds via Cationic Nb(V) Species
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(Arylimido)niobium(V) complexes containing 2-pyridylmethylanilido ligand Nb(NAr)X2(L) [L = 2-(2,6-Me2C6H3)NCH2(C5H4N); X = NMe2 (2a,b), OCH(CF3)2 (3a-c), Me (4a-c), CH2SiMe3 (5a); Ar = 2,6-Me2C6H3 (a), 2,6-iPr2C6H3 (b), 2-MeC6H4 (c)] have been prepared, and structures of 3a,b, 4b, and 5a were determined by X-ray crystallography. The dimethyl complexes (4a,b) exhibited catalytic activities for ethylene dimerization in the presence of methylaluminoxane (MAO), whereas the activity by 4c was negligible under the same conditions. Complex 4b showed the highest activity, and the activity at 50 °C was higher than those conducted at 25 and 80 °C. The major product was 1-butene, and 1-hexene was formed by subsequent reaction of ethylene with 1-butene accumulated in the reaction mixture. A first-order relationship between the activity [turnover frequency (TOF)] and ethylene pressure was observed, suggesting that the metal-alkyl species would play a role in this catalysis. The activities further increased remarkably upon addition of [Ph3C][B(C6F5)4] at 50 °C; TOF at the initial stage (5 min) of 2 100 000 h-1 (583 s-1) has been attained. Reactions of the dimethyl complexes (4a,b) with 1.0 equiv of [Ph3C][B(C6F5)4] in Et2O afforded [Nb(NAr)Me(L)]+[B(C6F5)4]-(Et2O)2 (6a,b), and the reaction of 6b with ethylene afforded 1-butene and 1-hexene even in the absence of MAO, clearly suggesting that the cationic species play a role in this catalysis. X-ray absorption near edge structure spectra of the catalyst solutions containing 4b (in toluene at 25 °C) and MAO (10 and 50 equiv) showed no significant differences in the pre-edge peak positions and intensities from that in the dimethyl complex (4b), strongly suggesting that both the oxidation states and the basic structures are maintained upon addition of MAO in these catalyst solutions.
- Kuboki, Masaharu,Nomura, Kotohiro
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supporting information
p. 1544 - 1559
(2019/04/17)
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- Supported palladium membrane reactor architecture for electrocatalytic hydrogenation
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Electrolytic palladium membrane reactors offer a means to perform hydrogenation chemistry utilizing electrolytically produced hydrogen derived from water instead of hydrogen gas. While previous embodiments of these reactors employed thick (≥25 μm) palladium foil membranes, we report here that the amount of palladium can be reduced by depositing a thin (1-2 μm) layer of palladium onto a porous polytetrafluoroethylene (PTFE) support. The supported palladium membrane can be designed to ensure the fast diffusion of reagent and hydrogen to the palladium layer. The hydrogenation of 1-hexyne, for example, shows that the supported Pd/PTFE membrane can achieve reaction rates (e.g., 0.71 mmol h-1) which are comparable to 0.92 mmol h-1 measured for palladium membranes with a high-surface area palladium electrocatalyst layer. The root cause of these comparable rates is that the high porosity of PTFE enables a 12-fold increase in electrocatalytic surface area compared to planar palladium foil membranes. These results provide a pathway for designing a cost-effective and potentially scalable electrolytic palladium membrane reactor.
- Delima, Roxanna S.,Sherbo, Rebecca S.,Dvorak, David J.,Kurimoto, Aiko,Berlinguette, Curtis P.
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p. 26586 - 26595
(2019/12/04)
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- α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization
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α-Diphenylphosphino-N-(pyrazin-2-yl)glycine was synthesized by the three-component condensation of diphenylphosphine, glyoxylic acid hydrate, and 2-aminopyrazine and its structure was confirmed by X-ray diffraction. It reacted with [Ni(COD)2] (COD is cycloocta-1,5-diene) to give complexes that were tested as catalysts for selective dimerization/oligomerization of ethylene to but-1-ene (main product) and C6–C14 α-olefins, respectively.
- Soficheva, Olga S.,Bekmukhamedov, Giyjaz E.,Dobrynin, Alexey B.,Heinicke, Joachim W.,Sinyashin, Oleg G.,Yakhvarov, Dmitry G.
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p. 575 - 577
(2019/11/02)
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- Catalyst Systems and Ethylene Oligomerization Method
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Disclosed herein is a catalyst system comprising (i) a heterocyclic 2-[(phosphinyl)aminyl]imine transition metal compound complex having Structure I wherein T is oxygen or sulfur, R1 and R2 are each independently a C1 to C20 organyl group consisting essentially of inert functional groups, R3 is hydrogen or a C1 to C20 organyl group, L is a C1 to C20 organylene group consisting essentially of inert functional groups, MXp represents a transition metal compound where M is a transition metal, X is a monoanion, and p is an integer from 1 to 6, Q is a neutral ligand, and q ranges from 0 to 6, and (ii) an organoaluminum compound. Also disclosed herein is a process comprising contacting (i) ethylene, (ii) a catalyst system comprising (a) a heterocyclic transition metal compound complex having Structure I as described herein and (b) an organoaluminum compound, and (iii) optionally hydrogen to form an oligomer product.
- -
-
Paragraph 0170-0172
(2019/06/14)
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- 1,5-Naphthyl-linked bis(imino)pyridines as binucleating scaffolds for dicobalt ethylene oligo-/polymerization catalysts: Exploring temperature and steric effects
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Six examples of dinuclear bis(imino)pyridine-cobalt(ii) complexes, [1,5-{2-(CMeN)-6-(CMeN(2,6-R12-4-R2-C6H2))C5H3N}2(C10H6)]Co2Cl4 (R1 = Me, R2 = H Co1; R1 = Et, R2 = H Co2; R1 = iPr, R2 = H Co3; R1 = Me, R2 = Me Co4; R1 = Et, R2 = Me Co5; R1 = CHPh2, R2 = Me Co6), have been prepared from the corresponding bis(tridentate) compartmental ligands (L1-L6) in reasonable yields. The molecular structures of Co3 and Co5 revealed two N,N,N-cobalt dichloride units to adopt anti-positions about the 1,5-naphthyl linking unit, with each cobalt center exhibiting a distorted trigonal bipyramidal geometry. On activation with either MAO or MMAO, Co1-Co6 were shown to promote both polymerization and oligomerization of ethylene with high overall activities (up to 1.03 × 107 gPE per·mol(Co) per·h for Co1/MAO at 70 °C). Curiously, on increasing the reaction temperature a larger proportion of polymer was noted, while at lower temperature an enhanced selectivity for oligomer was seen. In general, the oligomeric products displayed Schulz-Flory distributions with high selectivities for α-olefins (>99%). On the other hand, the highly linear polymers displayed narrow dispersities and comprised both fully saturated and unsaturated chain ends with the vinyl content (-CHCH2) found to rise with the reaction temperature. By modulating the steric hindrance exerted by the ortho-R1 substituents in the precatalyst, polyethylenes displaying a remarkably broad range of molecular weights could be obtained [from 4.52 kg mol-1 (R1 = Me) to 246.7 kg mol-1 (R1 = CHPh2)].
- Chen, Qiang,Suo, Hongyi,Zhang, Wenjuan,Zhang, Randi,Solan, Gregory A.,Liang, Tongling,Sun, Wen-Hua
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supporting information
p. 8264 - 8278
(2019/06/18)
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- Preparation of chromium catalysts bearing bispyridylamine and its performance in ethylene oligomerization
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A series of bispyridylamine ligands and chromium complexes designed for ethylene oligomerization have been synthesized, which was made up of both neutral organic ligand and inorganic anion. The compositions of these complexes have been fully characterized by spectroscopic and analytical methods. Catalysts (Cr1–Cr4) were evaluated in detail with methylaluminoxane (MAO) as an activator in the ethylene oligomerization. As a result, Cr1 achieved a higher catalytic activity of 2.93 × 105g/(mol(Cr) h) and a higher selectivity of 55.34% toward the valuable C8 compound using toluene as the solvent. The total selectivity to LAOs was 71.2%.
- Wang, Jun,Liu, Jinyi,Chen, Liduo,Lan, Tianyu,Wang, Libo
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p. 681 - 688
(2019/06/04)
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- Catalytic Properties of Chromium Complexes Based on 1,2-Bis(diphenylphosphino)benzene in the Ethylene Oligomerization Reaction
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Abstract: The activity of the catalyst systems of a number of diphosphine ligands and chromium complexes based on 1,2-bis(diphenylphosphino)benzene in the ethylene oligomerization reaction has been studied. Structural modifications of diphosphine ligands have been performed to create selective catalyst systems for ethylene oligomerization. It has been shown that the introduction of ortho-functional groups into one of the phenyl substituents at the phosphorus atom in diphosphine ligands makes it possible to carry out the process of ethylene oligomerization to 1-hexene with the selectivity of 90 wt % and above. One of the complexes (chromium complex 15) with a functionalized diphosphine ligand has been characterized by X-ray structure analysis. The influence of the change in the amount of the activator and its type on the activity of the catalyst systems has been studied. It has been shown that the replacement of some organoaluminum activator, methylaluminoxane, by trimethylaluminum does not decrease the productivity and selectivity of the catalyst systems based on diphosphine chromium complexes.
- Cheredilin,Sheloumov,Senin,Kozlova,Afanas’ev,Bespalova
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p. S72 - S87
(2020/01/23)
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- Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
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The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4?n (n=1–3) generates a disilane residue (MenSi2Cl6?n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.
- Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
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supporting information
p. 3809 - 3815
(2019/02/13)
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- Nickel-based ethylene oligomerization catalysts supported by PNSiP ligands
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A series of nickel (II) complexes bearing silicon bridged diphosphines ligands (PNSiP) have been synthesized and characterized. All nickel precatalysts, activated with ethylaluminum dichloride (EtAlCl2), exhibited moderate to high activities for ethylene dimerization to butylene. The in situ nickel precatalysts formed by mixing N-cyclopentyl-N-((diphenylphosphanyl)dimethylsilyl)-1,1-diphenylphosphanamine (L2) with NiBr2(DME) showed high catalytic activity (2.40 × 108 g/(molNi·h)) and high product selectivity (88.6%) towards butene using methylcyclohexane as solvent at 1.0?MPa ethylene pressure and 45°C temperature, no polyethylene(PE) was observed. Ligand backbone tuning of PNSiP-based catalytic systems help in precise understanding of steric bulk variation effects on catalytic performance.
- Huang, Yongwang,Zhang, Le,Wei, Wei,Alam, Fakhre,Jiang, Tao
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p. 363 - 368
(2018/02/06)
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- Copper-NHC-Mediated Semihydrogenation and Hydroboration of Alkynes: Enhanced Catalytic Activity Using Ring-Expanded Carbenes
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A series of two-coordinate copper tert-butoxide complexes bearing five-, six-, and seven-membered ring N-heterocyclic carbenes, prepared by protonolysis of (NHC)CuMes with tBuOH, have been used as catalytic precursors in the semihydrogenation of alkynes with silanes/tBuOH and the hydroboration of alkynes with HBPin. Both processes proceed with high regioselectivity and show enhancements with six- and seven-membered ring carbenes.
- Hall, Jonathan W.,Unson, Darcy M. L.,Brunel, Paul,Collins, Lee R.,Cybulski, Mateusz K.,Mahon, Mary F.,Whittlesey, Michael K.
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p. 3102 - 3110
(2018/09/12)
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- Accessing Frustrated Lewis Pair Chemistry through Robust Gold@N-Doped Carbon for Selective Hydrogenation of Alkynes
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Pyrolysis of Au(OAc)3 in the presence of 1,10-phenanthroline over TiO2 furnishes a highly active and selective Au nanoparticle (NP) catalyst embedded in a nitrogen-doped carbon support, Au@N-doped carbon/TiO2 catalyst. Parameters such as pyrolysis temperature, type of support, and nitrogen ligands as well as Au/ligand molar ratios were systematically investigated. Highly selective hydrogenation of numerous structurally diverse alkynes proceeded in moderate to excellent yield under mild conditions. The high selectivity toward the industrially important alkene substrates, functional group tolerance, and the high recyclability makes the catalytic system unique. Both high activity and selectivity are correlated with a frustrated Lewis pairs interface formed by the combination of gold and nitrogen atoms of N-doped carbon that, according to density functional theory calculations, can serve as a basic site to promote the heterolytic activation of H2 under very mild conditions. This "fully heterogeneous" and recyclable gold catalyst makes the selective hydrogenation process environmentally and economically attractive.
- Fiorio, Jhonatan Luiz,Gon?alves, Renato Vitalino,Teixeira-Neto, Erico,Ortu?o, Manuel A.,López, Núria,Rossi, Liane Marcia
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p. 3516 - 3524
(2018/04/14)
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- Additive-modulated switchable reaction pathway in the addition of alkynes with organosilanes catalyzed by supported Pd nanoparticles: Hydrosilylation: versus semihydrogenation
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We herein report supported Pd nanoparticles on N,O-doped hierarchical porous carbon as a single operation catalyst-enabled additive-modulated reaction pathway for alkynes addition with organosilanes between hydrosilyation and semihydrogenation. In the case of alkynes hydrosilylation, a simple iodide ion as an additive has a promotion effect on the activity and regio- and stereoselectivity, where iodide can coordinate with Pd NPs via strong δ donation to increase the electron density of the Pd atom, resulting in an increased ability for the oxidative addition of hydrosilane as the rate-determining step to make the reaction proceed efficiently to afford vinylsilanes in high yields with excellent regio- and stereoselectivity. For the catalytic transfer semihydrogenation of alkynes, water was introduced to mix with organosilane to form a silanol together with the generation of hydrogen atoms on the Pd NPs surface or the liberation of H2 gas as a reducing agent, whereby the quantitative reduction of alkynes was achieved with exclusive selectivity to alkenes. In both cases, the catalyst could be recycled several times without a significant loss in activity or selectivity. A broad range of alkyl and aryl alkynes with various functional groups are compatible with the reaction conditions. The role the additive exerted in each reaction was extensively investigated through control experiments as well as the kinetic isotopic effect along with spectroscopic characterization. In addition, the respective mechanism operating in both reactions was proposed.
- Duan, Yanan,Ji, Guijie,Zhang, Shaochun,Chen, Xiufang,Yang, Yong
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p. 1039 - 1050
(2018/03/05)
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