F:Flammable;111-65-9Relevant articles and documents
Production of Alcohols from Olefins via One-Pot Tandem Hydroformylation-Acetalization-Hydrogenolysis over Bifunctional Catalyst Merging RuIII-P Complex and RuIII Lewis Acid
Wang, Peng,Wang, Dong-Liang,Liu, Huan,Zhao, Xiao-Li,Lu, Yong,Liu, Ye
, p. 2404 - 2411 (2017)
A novel three-step tandem hydroformylation-acetalization-hydrogenolysis was first proposed to produce alcohols (derivatives) from olefins, and the developed unique Ru(III)-complex [Ru(III)-L2] ligated by the ionic diphosphine (L2) proved efficient toward this tandem reaction. In Ru(III)-L2, the strong π-acceptor nature of L2 guaranteed Ru-center remaining in +3 valence state without redox reaction. Hence, Ru(III)-L2 was able to behave as a bifunctional catalyst merging RuIII-P complex and RuIII Lewis acid, which acted not only as a transition metal catalyst responsible for hydroformylation of olefins and hydrogenolysis of (hemi)acetals but also as a Ru3+ Lewis acid in charge of acetalization of aldehydes [to form (hemi)acetals]. The easily performed acetalization served as a bridge step to get through the pathway from aldehydes to alcohols instead of the direct hydrogenation.
POLYMER-BOUND TITANIUM OLEFIN ISOMERIZATION CATALYSTS
Bergbreiter, David E.,Parsons, Gregory L.
, p. 47 - 54 (1981)
Polystyrene-bound bis(cyclopentadienyl)titanium dichloride has been shown to react with Grignard reagents to form a reactive alkene isomerization catalyst, which converts 1-alkenes primarily into E-2-alkenes at room temperature.The catalyst specificity se
Alkyne hydrogenation using Pd-Ag hybrid nanocatalysts in surface-immobilized dendrimers
Karakhanov, Edward A.,Maximov, Anton L.,Zolotukhina, Anna V.,Yatmanova, Nadezhda,Rosenberg, Edward
, p. 777 - 784 (2015)
A series of Pd-Ag mixed-metal nanocatalysts were prepared by reduction of Pd-Ag salts in the presence of poly(propylene imine) dendrimers, which were covalently bound to the surface of a silica polyamine composite, BP-1 (polyallylamine covalently bound to a silanized amorphous silica gel). Three different Pd-to-Ag ratios were evaluated (50:50, catalyst 1; 40:60, catalyst 2; 60:40, catalyst 3) with the goal of determining how the amount of Ag effects selectivity, rate and conversion in the selective reduction of alkynes, such as phenylacetylene and 1- or 4-octyne, to the corresponding alkenes. Conditions for the catalysis are reported where there is improved selectivity without a serious reduction in rate when compared with the analogous Pd-only catalysts. Catalyst 2 worked best for phenylacetylene and catalyst 3 worked best for the octynes. The catalysts could be reused seven times without loss of activity.
Production of linear alkane via hydrogenative ring opening of a furfural-derived compound in supercritical carbon dioxide
Chatterjee, Maya,Matsushima, Keichiro,Ikushima, Yutaka,Sato, Masahiro,Yokoyama, Toshirou,Kawanami, Hajime,Suzuki, Toshishige
, p. 779 - 782 (2010)
A simple method has been described to accomplish the formation of linear alkane with >99% selectivity in supercritical carbon dioxide under very mild conditions using Pd/Al-MCM-41 catalyst. The linear alakne was formed through the hydrogenation and dehydration/hydrogenation of 4-5-(5-(hydroxymethyl)furan-2- yl)but-3-en-2-one, which is an aldol condensation product of 5-hydroxymethyl furfural and acetone.
Catalytic and supported Barton-McCombie deoxygenation of secondary alcohols: A clean reaction
Boussaguet, Paul,Delmond, Bernard,Dumartin, Gilles,Pereyre, Michel
, p. 3377 - 3380 (2000)
Secondary alcohols were deoxygenated using a new version of the Barton- McCombie process involving a catalytic amount of supported tin hydride in the presence of trimethoxysilane. The products are then easily separated from the catalyst by a simple filtration avoiding pollution by toxic tin by-products. (C) 2000 ElSevier Science Ltd.
Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: Sorption and catalytic properties
Kozachuk, Olesia,Luz, Ignacio,Llabres I Xamena, Francesc X.,Noei, Heshmat,Kauer, Max,Albada, H. Bauke,Bloch, Eric D.,Marler, Bernd,Wang, Yuemin,Muhler, Martin,Fischer, Roland A.
, p. 7058 - 7062 (2014)
A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru II/III structural analogue of the well-known MOF family [M 3II,II(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the defective variants in the dissociative chemisorption of CO 2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins. The defect engineering in Ru-based metal-organic frameworks (MOFs) at coordinatively unsaturated metal centers (CUS) induces partial reduction of the metal nodes and leads to properties that are absent for the parent MOF, such as dissociative chemisorption of CO2 and enhanced sorption capacity of CO. The modified MOFs offer new perspectives as multifunctional materials whose performance is controlled by design of the defects.
Controlled Pyrolysis of Ni-MOF-74 as a Promising Precursor for the Creation of Highly Active Ni Nanocatalysts in Size-Selective Hydrogenation
Nakatsuka, Kazuki,Yoshii, Takeharu,Kuwahara, Yasutaka,Mori, Kohsuke,Yamashita, Hiromi
, p. 898 - 905 (2018)
Metal organic frameworks (MOFs) are a class of porous organic-inorganic crystalline materials that have attracted much attention as H2 storage devices and catalytic supports. In this paper, the synthesis of highly-dispersed Ni nanoparticles (NPs) for the hydrogenation of olefins was achieved by employing Ni-MOF-74 as a precursor. Investigations of the structural transformation of Ni species derived from Ni-MOF-74 during heat treatment were conducted. The transformation was monitored in detail by a combination of XRD, in situ XAFS, and XPS measurements. Ni NPs prepared from Ni-MOF-74 were easily reduced by the generation of reducing gases accompanied by the decomposition of Ni-MOF-74 structures during heat treatment at over 300 °C under N2 flow. Ni-MOF-74-300 exhibited the highest activity for the hydrogenation of 1-octene due to efficient suppression of excess agglomerated Ni species during heat treatment. Moreover, Ni-MOF-74-300 showed not only high activity for the hydrogenation of olefins but also high size-selectivity because of the selective formation of Ni NPs covered by MOFs and the MOF-derived carbonaceous layer.
Mechanism of the isomerization of 1-alkene during iron-catalyzed Fischer-Tropsch synthesis
Shi, Buchang,O'Brien, Robert J.,Bao, Shiqi,Davis, Burtron H.
, p. 202 - 208 (2001)
The deuterium/hydrogen exchange reaction was conducted under iron-catalyzed Fischer-Tropsch reaction conditions using a mixture of deuterated octane, nonane, decane, tridecane, and pentadecane as the probes. The deuterium/hydrogen exchange did not occur in alkanes under these conditions. Under the same reaction conditions, 1-octene-d16 was used as the probe to study the isomerization of 1-alkene. The 1-octene-d16 was reduced to deuterated octane, and isomerized to deuterated trans-2-octene and cis-2-octene with nearly equal amounts of the two isomers. Products from cracking and isomerization to internal octenes other than the 2-octene isomers did not occur to a measurable extent. When 1-octene-d16 was used as the probe, there was H/D exchange in octenes and octane; the lowest deuterium-containing isomer products were the d11 isotopomers, and there were no d16 isomers in the 2-octenes.
Hydrogenation of dienes by a recyclable poly(ethylene oxide)-rhodium phosphineless catalytic system
Tavares, Aline,Wolke, Silvana I.,da Rosa, Ricardo Gomes
, p. 374 - 382 (2008)
The monocationic complex [(η5-Cp*)2Rh2(μ2-Cl)3]PF6 in poly(ethylene oxide) (PEO) 3350/MeOH has proven to be a very efficient catalyst for 1,7-octadiene, 1,9-decadiene, and 1,5-cyclooctadiene hydrogenation. This system allows perfect product separation and catalyst phase recycling, resulting in thousands of catalytic cycles (TON ≈ 9000). Even at room temperature, turnover frequencies as high as 5000 h-1 are attained (50 bar), which makes this one of the most active catalytic systems for diene hydrogenation. Kinetic studies reveal that the reaction rate is second-order in H2 pressure and first-order in both rhodium and diene concentrations. Typical tests suggest that, despite the reductive reaction conditions, which could lead to colloidal metal dispersion, the reduction of dienes is catalyzed by molecular species.
Reductive-hydroformylation of 1-octene to nonanol using fibrous Co3O4 catalyst
Bhagade, Sachin S.,Chaurasia, Shivkumar R.,Bhanage, Bhalchandra M.
, p. 147 - 152 (2018)
This work reports, reductive-hydroformylation of 1-octene to nonanol in the presence of fine fibrous cobalt oxide (Co3O4) nano-catalyst prepared via urea reduction method under phosphine-free and additive free condition. Co3O4 nano-catalyst was prepared by the wet chemical method and was characterized using various instrumental techniques like FEG-SEM, EDS, XRD, TPR and FTIR. The effects of various reaction parameters such as temperature, synthesis gas (CO/H2) pressure/ratio, catalyst loading, solvent and time were studied. The reaction was successfully achieved in tetrahydrofuran (THF) as the solvent medium. This reaction believed to takes place through the generation of HCox(CO)y active catalyst species. The Co3O4 nano-catalyst could be recycled up to three consecutive cycles.
