110-54-3Relevant articles and documents
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Brown,Brown
, p. 2827 (1962)
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Regio- and Chemoselective Hydrogenation of Dienes to Monoenes Governed by a Well-Structured Bimetallic Surface
Miyazaki, Masayoshi,Furukawa, Shinya,Komatsu, Takayuki
, p. 18231 - 18239 (2017)
Unprecedented surface chemistry, governed by specific atomic arrangements and the steric effect of ordered alloys, is reported. Rh-based ordered alloys supported on SiO2 (RhxMy/SiO2, M = Bi, Cu, Fe, Ga, In, Pb, Sn, and Zn) were prepared and tested as catalysts for selective hydrogenation of trans-1,4-hexadiene to trans-2-hexene. RhBi/SiO2 exhibited excellent regioselectivity for the terminal C=C bond and chemoselective hydrogenation to the monoene, not to the overhydrogenated alkane, resulting in a high trans-2-hexene yield. Various asymmetric dienes, including terpenoids, were converted into the corresponding inner monoenes in high yields. This is the first example of a regio- and chemoselective hydrogenation of dienes using heterogeneous catalysts. Kinetic studies and density functional theory calculations revealed the origin of the high selectivity: (1) one-dimensionally aligned Rh arrays geometrically limit hydrogen diffusion and attack to alkenyl carbons from one direction and (2) adsorption of the inner C=C moiety to Rh is inhibited by steric repulsion from the large Bi atoms. The combination of these effects preferentially hydrogenates the terminal C=C bond and prevents overhydrogenation to the alkane.
Direct Reduction of 1-Bromo-6-chlorohexane and 1-Chloro-6-iodohexane at Silver Cathodes in Dimethylformamide
Rose, John A.,McGuire, Caitlyn M.,Hansen, Angela M.,Karty, Jonathan A.,Mubarak, Mohammad S.,Peters, Dennis G.
, p. 311 - 317 (2016)
Cyclic voltammetry and controlled-potential (bulk) electrolyses have been employed to probe the electrochemical reductions of 1-bromo-6-chlorohexane and 1‐chloro-6-iodohexane at silver cathodes in dimethylformamide (DMF) containing 0.050?M tetra-n-butylammonium tetrafluoroborate (TBABF4). A cyclic voltammogram for reduction of 1-bromo-6-chlorohexane shows a single major irreversible cathodic peak, whereas reduction of 1-chloro-6-iodohexane gives rise to a pair of irreversible cathodic peaks. Controlled-potential (bulk) electrolyses of 1-bromo-6-chlorohexane at a silver gauze cathode reveal that the process involves a two-electron cleavage of the carbon–bromine bond to afford 1-chlorohexane as the major product, along with 6-chloro-1-hexene, n‐hexane, 1‐hexene, and 1,5-hexadiene as minor species. In contrast, bulk electrolyses of 1-chloro-6-iodohexane indicate that the first voltammetric peak corresponds to a one-electron process, leading to production of a dimer (1,12-dichlorododecane) together with 1-chlorohexane and 6-chloro-1-hexene as well as 1‐hexene and 1,5-hexadiene in trace amounts. At potentials corresponding to the second cathodic peak, reduction of 1-chloro-6-iodohexane is a mixture of one- and two-electron steps that yields the same set of products, but in different proportions. Mechanistic schemes are proposed to explain the electrochemical behavior of both 1‐bromo-6-chlorohexane and 1-chloro-6-iodohexane.
Calcium Hydride Cation [CaH]+ Stabilized by an NNNN-type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation
Schuhknecht, Danny,Lhotzky, Carolin,Spaniol, Thomas P.,Maron, Laurent,Okuda, Jun
, p. 12367 - 12371 (2017)
Reaction of dibenzyl calcium complex [Ca(Me4TACD)(CH2Ph)2], containing the neutral NNNN-type macrocyclic ligand Me4TACD (Me4TACD=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane), with triphenylsilane gave the cationic dinuclear calcium hydride [Ca2H2(Me4TACD)2](PhCHSiPh3)2 which was characterized by NMR spectroscopy and single-crystal X-ray diffraction. The cation can be regarded as the ligand-stabilized dimeric form of hypothetical [CaH]+. Hydrogenolysis of benzyl calcium cation [Ca(Me4TACD)(CH2Ph)(thf)]+ gave dicationic calcium hydrides [Ca2H2(Me4TACD)2][BAr4]2 (Ar=C6H4-4-tBu; C6H3-3,5-Me2) containing weakly coordinating anions. In THF, they catalyzed the isotope exchange of H2 and D2 to give HD and the hydrogenation of unactivated 1-alkenes.
Biphasic hydroformylation of 1-hexene with carbon dioxide catalyzed by ruthenium complex in ionic liquids
Tominaga, Ken-Ichi,Sasaki, Yoshiyuki
, p. 14 - 15 (2004)
Hydroformylation of 1-hexene using carbon dioxide as carbonyl carbon source attained high yield and good chemoselectivity in heptanols when a ruthenium complex was used in biphasic ionic liquid-toluene system.
Cationic pyridyl(benzoazole) ruthenium(II) complexes: Efficient and recyclable catalysts in biphasic hydrogenation of alkenes and alkynes
Ogweno, Aloice O.,Ojwach, Stephen O.,Akerman, Matthew P.
, p. 250 - 258 (2014)
The synthesis, structural characterization of cationic 2-(2-pyridyl)benzoazole)ruthenium(II) complexes and their applications in biphasic hydrogenations of alkenes is reported. Reactions of 2-(2-pyridyl)benzoimidazole (L1), 2-(2-pyridyl)benzothiazole (L2) and 2-(2-pyridyl)benzoxazole (L3) with [η6-(2-phenoxyethanol)RuCl2]2produced the corresponding cationic complexes [η6-(2-phenoxyethanol)RuCl(L1)]Cl (1), [η6-(2-phenoxyethanol)RuCl(L2)]Cl (2) and [η6-(2-phenoxyethanol)RuCl(L3)]Cl (3) in good yields. Solid state structures of 1-3 confirmed the bidentate coordination modes of L1-L3 and formation of cationic species through displacement of one chloride ligand from Ru(II) coordination sphere. Complexes 1-3 produced active catalysts for high pressure hydrogenation of alkenes both in methanol and biphasic conditions. Relatively lower activities were observed in the hydrogenation of terminal alkynes giving a mixture of alkane and alkene products. Complexes 1-3 were recyclable under biphasic conditions and retained significant catalytic activities in six cycles. Reaction parameters such as substrate/catalyst ratio, temperature, and aqueous/organic ratio affected the catalytic trends.
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Greenfield et al.
, p. 1258 (1954)
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Pd Nanocubes@ZIF-8: Integration of Plasmon-Driven Photothermal Conversion with a Metal-Organic Framework for Efficient and Selective Catalysis
Yang, Qihao,Xu, Qiang,Yu, Shu-Hong,Jiang, Hai-Long
, p. 3685 - 3689 (2016)
Composite nanomaterials usually possess synergetic properties resulting from the respective components and can be used for a wide range of applications. In this work, a Pd nanocubes@ZIF-8 composite material has been rationally fabricated by encapsulation of the Pd nanocubes in ZIF-8, a common metal-organic framework (MOF). This composite was used for the efficient and selective catalytic hydrogenation of olefins at room temperature under 1 atm H2 and light irradiation, and benefits from plasmonic photothermal effects of the Pd nanocube cores while the ZIF-8 shell plays multiple roles; it accelerates the reaction by H2 enrichment, acts as a "molecular sieve" for olefins with specific sizes, and stabilizes the Pd cores. Remarkably, the catalytic efficiency of a reaction under 60 mW cm-2 full-spectrum or 100 mW cm-2 visible-light irradiation at room temperature turned out to be comparable to that of a process driven by heating at 50 °C. Furthermore, the catalyst remained stable and could be easily recycled. To the best of our knowledge, this work represents the first combination of the photothermal effects of metal nanocrystals with the favorable properties of MOFs for efficient and selective catalysis.
TRANSFORMATIONS OF n-HEXANE AND 1-HEXENE ON ALUMINUM, GALLIUM, AND INDIUM OXIDES
Bryukhanov, V. G.,Rozengart, M. I.,Isagulyants, G. V.
, p. 613 - 616 (1980)
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Further studies of the PtII/SnCl2 catalyzed hydroformylation
Scrivanti, A.,Paganelli, S.,Matteoli, U.,Botteghi, C.
, p. 439 - 446 (1990)
A convenient synthesis of the complexes trans- and trans- is described, and their NMR spectra in the presence of SnCl2 are discussed.These complexes have been examined as catalysts in 1-hexene hydroformylation in the presence of an excess of SnCl2.Their catalytic behaviour is compared with that of the systems based on complexes trans-, trans-, trans-, and cis-.
Heterolytic H2 activation on a carbene-ligated rhodathiaborane promoted by isonido-nido cage opening
Calvo, Beatriz,Macias, Ramon,Polo, Victor,Artigas, Maria Jose,Lahoz, Fernando J.,Oro, Luis A.
, p. 9863 - 9865 (2013)
A new mechanism of H2 activation is reported to occur on a carbene-ligated rhodathiaborane that features metal-thiaborane bifunctional synergistic effects. The key is the creation of vacant coordination sites by an isonido-nido structural transformation leading to the heterolytic H-H bond splitting.
Development of silica-supported frustrated Lewis pairs: Highly active transition metal-free catalysts for the Z-selective reduction of alkynes
Szeto, Kai C.,Sahyoun, Wissam,Merle, Nicolas,Castelbou, Jessica Llop,Popoff, Nicolas,Lefebvre, Frédéric,Raynaud, Jean,Godard, Cyril,Claver, Carmen,Delevoye, Laurent,Gauvin, Régis M.,Taoufik, Mostafa
, p. 882 - 889 (2016)
Supported Lewis acid/base systems based on a triphenyl phosphine fragment and Piers' reagent (HB(C6F5)2) or BArF have been prepared and characterized. Both materials show unprecedented catalytic activity in the Z-selective hydrogenation of 3-hexyne to Z-3-hexene with a selectivity up to 87%. Other alkynes can also be hydrogenated Z-selectively, albeit with moderate yields. The activity of the supported phosphine/HB(C6F5)2 adduct is similar to the only homogeneous example reported thus far based on bridged B/N frustrated Lewis pairs under high hydrogen pressure. Importantly, this transition metal-free supported catalyst was recycled five times in the challenging selective hydrogenation of a non-polar unactivated alkyne.
Investigation of a system of protecting layer for the process of hydrorefining oily distillates of Uzbekistan's petroleum
Yunusov,Molodozhenyuk,Ergashev,Dzhalalova,Gashenko,Saidulaev
, p. 1207 - 1212 (2007)
Complex investigation is conducted, directed to development of contacting materials (forcontacts) and catalysts for the protecting layer in the process of hydrorefining petroleum distillates taking into account their specificity and extensively attracting local raw materials. Forcontact FZS-7 is developed which, besides the function of uniform distribution of crude material over the reactor section, diminishes tarring and performs, owing to low nickel content, mild hydrogenation of unsaturated compounds. The proposed kaolin-bset catalyst of the protecting layer with low content of molybdenum oxide works reliably with the residual crude material with high content of iron and displays high enough demetallization activity.
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Habeeb,Tuch
, p. 696 (1976)
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Brown,Murray
, p. 4108 (1959)
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STUDY OF THE CATALYTIC ACTIVITY OF METAL COMPLEXES FIXED ON SOLID SUPPORTS. 7. SYNTHESIS OF Pd-Sn COMPLEXES ATTACHED TO MACROPOROUS ANION EXCHANGERS AND STUDY OF THEIR ACTIVITY IN THE HYDROGENATION OF 1-HEXENE
Sharf, V. Z.,Panfilova, L. D.,Borunova, N. V.,Antseva, N. V.,Karapetyan, L. P.,et al.
, p. 695 - 698 (1989)
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Electrochemical Reduction of 1,6-Dihalohexanes at Carbon Cathodes in Dimethylformamide
Mubarak, Mohammad S.,Peters, Dennis G.
, p. 681 - 685 (1995)
Cyclic voltammograms for the reduction of 1,6-dibromo-, 1,6-diiodo-, 1-bromo-6-chloro-, and 1-chloro-6-iodohexane at glassy carbon electrodes in dimethylformamide containing tetramethylammonium perchlorate exhibit single irreversible waves that correspond to the reductive cleavage of carbon-bromine or carbon-iodine bonds.When large-scale controlled-potential electrolyses of either 1,6-dibromo- or 1,6-diiodohexane are performed at reticulated vitreous carbon, the principal products are n-hexane (30-45percent), 1-hexene (28-34percent), 1,5-hexadiene (6-16percent), and cyclohexane (7percent), with n-dodecane being another significant species obtained from 1,6-diiodohexane.Because a carbon-chlorine bond is not directly reducible, 1-bromo-6-chloro- and 1-chloro-5-iodohexane give rise mainly to 1-chlorohexane (47-64percent), 6-chloro-1-hexene (20-33percent), and 1,12-dichlorododecane (2-25percent).From these product distributions, and with the aid of experiments done in the presence of deuterium-labeled reagents, we conclude that the electrolytic reduction of 1,6-diiodo- and 1-chloro-6-iodohexane involves both radical and carbanion intermediates, whereas only carbanionic pathways are important for electrolyses of 1,6-dibromo- and 1-bromo-6-chlorohexane.
Decarboxylation and further transformation of oleic acid over bifunctional, Pt/SAPO-11 catalyst and Pt/chloride Al2O3 catalysts
Ahmadi, Masoudeh,Macias, Eugenia E.,Jasinski, Jacek B.,Ratnasamy, Paul,Carreon, Moises A.
, p. 14 - 19 (2014)
Catalytic decarboxylation and further conversion of oleic acid to branched and aromatic hydrocarbons in a single process step, over Pt-SAPO-11 and Pt/chloride Al2O3 is presented. An increase of both reaction time and temperature increase the selectivity to heptadecane. Higher selectivity to heptadecane was observed in the presence of hydrogen. Decarboxylation of oleic acid was as high as ~98 wt% (selectivity for heptadecane >30%) at 325 C in the presence of hydrogen. Branched isomers, alkyl aromatics, like dodecyl benzene and cracked (17) paraffins were the other products.
Effects of Catalyst Site Accessibility on Catalysis by Rhodium(I) Complexes of Amphiphilic Ligands (1+) (n = 2,3,6,or 10) tethered to a Cation-exchange Resin
Renaud, Eric,Baird, Michael C.
, p. 2905 - 2906 (1992)
The effects of catalyst site accessibility on the activities of supported olefin hydrogenation catalysts have been assessed utilizing the complexes 3 4-norbornadiene; L = Ph2P(CH2)nPMe3(1+); n = 2, 3, 6 or 10> tethered to a cation-exchange resin via the tetraalkylphosphonium moieties of the co-ordinated ligands; the most active catalysts are those containing the longer-chain ligands, where the catalyst sites are farthest removed from steric hindrance by the resin surface.
Cryosynthesis of catalysts for propylene oligomerization based on titanium tetrachloride and magnesium
Tarkhanova,Smirnov,Tsvetkova,Tjurina
, p. 891 - 894 (1999)
A highly dispersed catalyst for oligo- and polymerization of propylene was synthesized by the interaction of TiCl4 with magnesium in the cocondensates of their vapor with benzene and pentane. The catalyst contains MgCl2 and organotitanium and organomagnesium cluster derivatives. The transformations of propylene and hex-1-ene over the catalysts were studied. The direction of catalytic reactions and activity of the catalyst depend on the TiCl4 : Mg molar ratio and the hydrocarbon used. Systems with an equimolar ratio of the reactants obtained in a benzene matrix exhibit the highest activity. Propylene oligomers containing a considerable fraction of unsaturated bonds are formed in the presence of the catalysts at room temperature and a pressure of 300 Torr.
Artificial metalloenzymes via encapsulation of hydrophobic transition-metal catalysts in surface-crosslinked micelles (SCMs)
Zhang, Shiyong,Zhao, Yan
, p. 9998 - 10000 (2012)
Encapsulation of a hydrophobic rhodium catalyst in crosslinked micelles allowed nonpolar substrates to react in water with unusual selectivity. This journal is The Royal Society of Chemistry 2012.
Hydrogenation of unsaturated hydrocarbons catalyzed by homogeneous and supported Rh, Rh-Co, and Pd, Pd-Ni complexes with oligomeric allene ligands
Khar'kova,Rozantseva,Frolov
, p. 214 - 219 (2010)
Mono-and bimetallic Rh and Rh-Co complexes containing oligoallene ligands were synthesized. Their catalytic activity was examined in the hydrogenation of unsaturated compounds, such as isoprene, hexene-1, and toluene. The catalytic activity of Rh(DMA)ol and Rh-Co(DMA)ol was shown to be 16 800 and 23000 mol/(mol h) in the hydrogenation of hexene-1 and 72 and 90 mol/(mol h) in the hydrogenation of toluene, respectively. Isoprene is hydrogenated completely: the rate curves exhibit two portions corresponding to hydrogenation of both double bonds. The catalytic activity of palladium oligodimethylallene complexes deposited on an inorganic support (γ-Al 2O3) in isoprene hydrogenation depends on the support preparation procedure, the particle size, and the metal loading on the surface. Heterogenization of the homogeneous mono-and bimetallic Rh and Pd complexes somewhat enhances the catalytic activity in hydrogenation of the given substrates. Pleiades Publishing, Ltd., 2010.
Ruthenium carbonyl carboxylates with nitrogen containing ligands: IV. Catalytic activity in the hydroformylation of olefins in homogeneous phase 1
Frediani, Piero,Bianchi, Mario,Salvini, Antonella,Carluccio, Luciano C.,Rosi, Luca
, p. 35 - 40 (1997)
Ruthenium carbonyl acetato complexes containing bipyridines or phenantrolines ligands are tested as catalysts in the hydroformylation of hex-1-ene in homogeneous phase. These catalysts are active also in solutions containing water and the selectivity to aldehyde is high. Only a moderate hydrogenation of the alkene occurs. The regioselectivity to the linear aldehyde reaches 85.7% when using the mononuclear complex containing 4,7-dmphen as ligand. In the course of the reaction the starting olefm is largely isomerized.
The catalytic activity of alkali metal alkoxides and titanium alkoxides in the hydrosilylation of unfunctionalized olefins
Yang, Xiaoling,Bai, Ying,Li, Jiayun,Liu, Yu,Peng, Jiajian,Li, Tianbo,Lang, Rui,Qiao, Botao
, p. 83 - 86 (2019)
The catalytic activities of titanium alkoxides and alkali metal alkoxides for hydrosilylation of unfunctionalized olefins have been studied. Titanium(IV) alkoxides showed excellent catalytic activity, while alkali metal alkoxides have low catalytic activity for the hydrosilylation of olefins. However, by using titanocene dichloride as an additive, alkali metal alkoxides showed also excellent catalytic property for hydrosilylation. In comparison with titanium alkoxides, no α-adduct was obtained by using alkali metal alkoxides/Cp2TiCl2 as catalysts.
KINETICS OF HYDROGENATION OF 1-HEXENE IN THE PRESENCE OF AROMATIC HYDROCARBONS ON PALLADIUM SULFIDE CATALYST
Matveeva, T. M.,Nekrasov, N. V.,Kostyukovskii, M. M.,Navalikhina, M. D.,Krichko, A. A.,Kiperman, S. L.
, p. 1104 - 1110 (1982)
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Fabricating nickel phyllosilicate-like nanosheets to prepare a defect-rich catalyst for the one-pot conversion of lignin into hydrocarbons under mild conditions
Cao, Meifang,Chen, Bo,He, Chengzhi,Ouyang, Xinping,Qian, Yong,Qiu, Xueqing
supporting information, p. 846 - 857 (2022/02/09)
The one-pot conversion of lignin biomass into high-grade hydrocarbon biofuels via catalytic hydrodeoxygenation (HDO) holds significant promise for renewable energy. A great challenge for this route involves developing efficient non-noble metal catalysts to obtain a high yield of hydrocarbons under relatively mild conditions. Herein, a high-performance catalyst has been prepared via the in situ reduction of Ni phyllosilicate-like nanosheets (Ni-PS) synthesized by a reduction-oxidation strategy at room temperature. The Ni-PS precursors are partly converted into Ni0 nanoparticles by in situ reduction and the rest remain as supports. The Si-containing supports are found to have strong interactions with the nickel species, hindering the aggregation of Ni0 particles and minimizing the Ni0 particle size. The catalyst contains abundant surface defects, weak Lewis acid sites and highly dispersed Ni0 particles. The catalyst exhibits excellent catalytic activity towards the depolymerization and HDO of the lignin model compound, 2-phenylethyl phenyl ether (PPE), and the enzymatic hydrolysis of lignin under mild conditions, with 98.3% cycloalkane yield for the HDO of PPE under 3 MPa H2 pressure at 160 °C and 40.4% hydrocarbon yield for that of lignin under 3 MPa H2 pressure at 240 °C, and its catalytic activity can compete with reported noble metal catalysts.
Conversion of Phenol and Lignin as Components of Renewable Raw Materials on Pt and Ru-Supported Catalysts
Bobrova, Nataliia A.,Bogdan, Tatiana V.,Bogdan, Viktor I.,Koklin, Aleksey E.,Mishanin, Igor I.
, (2022/03/01)
Hydrogenation of phenol in aqueous solutions on Pt-Ni/SiO2, Pt-Ni-Cr/Al2 O3, Pt/C, and Ru/C catalysts was studied at temperatures of 150–250? C and pressures of 40–80 bar. The possibility of hydrogenation of hydrolysis lignin in an aqueous medium in the presence of a Ru/C catalyst is shown. The conversion of hydrolysis lignin and water-soluble sodium lignosulfonate occurs with the formation of a complex mixture of monomeric products: a number of phenols, products of their catalytic hydrogenation (cyclohexanol and cyclohexanone), and hydrogenolysis products (cyclic and aliphatic C2 –C7 hydrocarbons).
Photo-Initiated Cobalt-Catalyzed Radical Olefin Hydrogenation
Sang, Sier,Unruh, Tobias,Demeshko, Serhiy,Domenianni, Luis I.,van Leest, Nicolaas P.,Marquetand, Philipp,Schneck, Felix,Würtele, Christian,de Zwart, Felix J.,de Bruin, Bas,González, Leticia,V?hringer, Peter,Schneider, Sven
, p. 16978 - 16989 (2021/08/09)
Outer-sphere radical hydrogenation of olefins proceeds via stepwise hydrogen atom transfer (HAT) from transition metal hydride species to the substrate. Typical catalysts exhibit M?H bonds that are either too weak to efficiently activate H2 or too strong to reduce unactivated olefins. This contribution evaluates an alternative approach, that starts from a square-planar cobalt(II) hydride complex. Photoactivation results in Co?H bond homolysis. The three-coordinate cobalt(I) photoproduct binds H2 to give a dihydrogen complex, which is a strong hydrogen atom donor, enabling the stepwise hydrogenation of both styrenes and unactivated aliphatic olefins with H2 via HAT.