108-08-7Relevant articles and documents
Ring-opening of Alkyl-substituted Cyclopropanes in the Presence of Hydrogen on Copper
Bartok, Mihaly,Palinko, Istvan,Molnar, Arpad
, p. 953 - 954 (1987)
In the presence of hydrogen on copper, the cyclopropanes (1), (2), and (3) are transformed into saturated hydrocarbons containing the same number of carbon atoms (alkenes are also formed, through isomerization of the cyclopropanes); these studies reveal the importance of a previously unknown property of copper in heterogeneous metal catalysis.
Activation and isomerization of hydrocarbons over WO3/ZrO2 catalysts. II. Influence of tungsten loading on catalytic activity: Mechanistic studies and correlation with surface reducibility and tungsten surface species
Di Gregorio, Francois,Keller, Nicolas,Keller, Valerie
, p. 159 - 171 (2008)
We studied the correlation among the catalytic behavior of WO3/ZrO2 samples toward unsaturated and saturated hydrocarbons transformation, tungsten surface species oxidation states, and the crystallographic structure of the zirconia support. Different tungsten-loaded catalysts were studied, from 9 wt% (near-monolayer coverage) to 30 wt%. The resulting WO3/ZrO2 materials were obtained by impregnation of a tungsten salt on either a commercially available monoclinic zirconia or an amorphous hydroxide, ZrOx(OH)4-2x, followed by a calcination step (according to the Hino and Arata procedure), leading to a tetragonal structure. In contrast to previous works, here we demonstrate that the crystallographic structure of zirconia has no influence on catalytic properties. Correlations with XPS analyses revealed two aspects of catalytic behavior that depend strongly on the catalyst reducibility and thus on the W surface species oxidation states. First, on hardly reducible (tungsten loadings a purely acidic monomolecular mechanism for both isomerization (largely predominant) and cracking reactions, associated with W6+ and W5+ surface species, was demonstrated. Second, on easily reducible (tungsten loadings >15 wt%) or deeply reduced (over 723 K) surfaces, a bifunctional mechanism associating dehydrogenating/hydrogenating properties occurring on metallic tungsten and acidic isomerization and cracking on W5+ and W6+ surface species was observed. However, in this last case, we could not exclude the participation of a purely metallic isomerization mechanism occurring through σ-alkyl adsorbed species on the β-W metallic phase. A more pronounced reduction then led to an increase in the extensive hydrogenolysis mechanism, causing catalyst deactivation.
Calingaert,Flood
, p. 956 (1935)
Sakai et al.
, p. 696,697, 699 (1975)
Mechanism of Isomerization of Hydrocarbons on Metals. Part 9.-Isomerization and Dehydrocyclization of 2,3-Dimethyl(2-(13)C)pentane on a 10percent Pt-Al2O3 Catalyst
Parayre, Patrick,Amir-Ebrahimi, Valia,Gault, Francois G.,Frennet, Alfred
, p. 1704 - 1722 (1980)
The isomerization, dehydrocyclization and hydrogenolysis of 2,3-dimethyl(2-(13)C)pentane have been studied at 260 deg C over a 10percent Pt-Al2O3 catalyst of low dispersion, under various hydrocarbon and hydrogen pressures.Most of the isomerization products are accounted for either by a bond-shift mechanism or by a cyclic mechanism involving 1,2-dimethylcyclopentane intermediate.The absence of significant scrambling of the label suggests that the rate-determining step in isomerization is the skeletal rearrangement of highly dehydrogenated species.The positive order as a function of hydrogen which is found (0.8-1.2) cannot then be taken as evidence that desorption is rate-determining.It is best explained by assuming multisite adsorption of hydrocarbon and competition with hydrogen for chemisorption on the same sites.The results provide argument in favour of a reactive rather than dissociative-type adsorption step.
Mechanism of Isomerization of Hydrocarbons on Metals. Part 11.-Isomerization and Dehydrocyclization of (13)C-labelled 3-Methylhexanes on Pt-Al2O3 Catalysts
Amir-Ebrahimi, Valia,Gault, Francois G.
, p. 1735 - 1756 (1980)
The isomerization, dehydrocyclization and hydrogenolysis of 3-methylhexane have been studied at 320-380 deg C over a series of Pt-Al2O3 catalysts with a metal dispersion extending from 0.05 to 1.The use of five labelled compounds, 3-methyl(1-(13)C), (2-(13)C), (3-(13)C), (6-(13)C)hexanes and 3-methyl((13)C)hexane, alloved distinction between the various parallel pathways.On all catalysts the predominant reaction was the isomerization according to a cyclic mechanism involving either 1,3-dimethyl-, 1,2-dimethyl- or ethyl-cyclopentane intermediates with a relative contribution of 60, 40 and 20 percent, respectively.These results are consistent wiith a dehydrocyclization scheme involving a metallocarbene as precursor and dicarbene or dicarbyne recombination as the rate-determining step.
Silica-supported dendrimer-palladium complex-catalyzed selective hydrogenation of dienes to monoolefins
Zweni, Pumza P.,Alper, Howard
, p. 725 - 731 (2006)
The selective hydrogenation of cyclic and acyclic dienes to monoolefins occurs under very mild conditions, in the presence of silica-supported PAMAM-Pd complexes. The activity and selectivity of this reaction is sensitive to the dendrimer structure. These dendritic complexes display excellent recycle properties, retaining activity for up to eight recycles.
Alkanethiolate-capped palladium nanoparticles for selective catalytic hydrogenation of dienes and trienes
Chen, Ting-An,Shon, Young-Seok
, p. 4823 - 4829 (2017)
Selective hydrogenation of dienes and trienes is an important process in the pharmaceutical and chemical industries. Our group previously reported that the thiosulfate protocol using a sodium S-alkylthiosulfate ligand could generate catalytically active Pd nanoparticles (PdNP) capped with a lower density of alkanethiolate ligands. This homogeneously soluble PdNP catalyst offers several advantages such as little contamination via Pd leaching and easy separation and recycling. In addition, the high activity of PdNP allows the reactions to be completed under mild conditions, at room temperature and atmospheric pressure. Herein, a PdNP catalyst capped with octanethiolate ligands (C8 PdNP) is investigated for the selective hydrogenation of conjugated dienes into monoenes. The strong influence of the thiolate ligands on the chemical and electronic properties of the Pd surface is confirmed by mechanistic studies and highly selective catalysis results. The studies also suggest two major routes for the conjugated diene hydrogenation: the 1,2-addition and 1,4-addition of hydrogen. The selectivity between two mono-hydrogenation products is controlled by the steric interaction of substrates and the thermodynamic stability of products. The catalytic hydrogenation of trienes also results in the almost quantitative formation of mono-hydrogenation products, the isolated dienes, from both ocimene and myrcene.
A novel route for the synthesis of alkanes from glycerol in a two step process using a Pd/SBA-15 catalyst
Udayakumar,Pandurangan
, p. 78719 - 78727 (2015/10/05)
Glycerol is produced as a valuable by-product in the transesterification of fatty acids, but it cannot be used directly as a fuel additive. In this study, we developed a systematic conversion for glycerol, which proceeds via synthesizing the key intermediate, 1,2,3-tribromopropane and using the Suzuki coupling reaction to introduce the alkyl group. A series of Pd/SBA-15 catalysts with different wt% of Pd (10%, 15% and 20%) was prepared by a one step sol-gel method. The structure and composition of the catalysts were characterized by X-ray diffraction analysis (XRD), N2 adsorption-desorption isotherms, transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectrometry (ICP-OES). The metallic state of dispersed palladium in SBA-15 is confirmed with X-ray photoelectron spectroscopy (XPS). Pd/SBA-15 with a Pd loading of 20 wt% shows good catalytic activity at 90 °C with methylboronic acid, allowing the complete conversion of 1,2,3-tribromopropane and 64% selectivity of 3-methylpentane. The optimized catalysts were also employed in coupling reactions between various alkylhalides and methylboronic acid, which obtained the desired product with an excellent selectivity. The catalyst can be successfully recycled five times. After the first cycle, we observed a drop in activity with 20% Pd/SBA-15, which was due to the leaching of palladium but in the later cycles, there was no significant decrease in activity.
A novel iron complex for cross-coupling reactions of multiple C-Cl bonds in polychlorinated solvents with grignard reagents
Gartia, Yashraj,Pulla, Sharon,Ramidi, Punnamchandar,Farris, Carolina Costa,Nima, Zeid,Jones, Darin E.,Biris, Alexandru S.,Ghosh, Anindya
, p. 1397 - 1404 (2013/01/15)
A novel iron(III) complex (2) of a pincer ligand [1, N2,N6-bis(2,6- diisopropylphenyl)pyridine-2,6-dicarboxamide] was developed and used for remediation of polychlorinated solvents via sp3-sp3 coupling of Grignard reagents with C-Cl bonds. The use of an iron catalyst for such coupling reactions is highly desirable due to its greener and more economical nature. Complex 2 was characterized using various spectroscopic techniques: electrospray ionization mass spectrometer (ESI-MS, m/z 575.1), cyclic voltammetry (E 1/2, 0.03 V and ΔE, 0.97 V), and ultraviolet visible (UV/Vis) spectroscopic techniques. The iron(III) complex showed efficient activation of multiple C-Cl bonds and catalyzing C-C coupling of polychlorinated alkyl halides, such as dichloromethane (CH2Cl2), chloroform (CHCl3), and carbon tetrachloride (CCl4), with various Grignard reagents under ambient reaction conditions. Complex 2 showed exceptional activity with reactions approaching near completion in about 5 min. With the required catalyst loading as low as 0.2 mol%, considerably high turnover numbers (TON = 483) and turnover frequency (TOF = 5,800 h-1) were obtained. None of the products detected during the reaction contained any chlorine, indicating an efficient dechlorination method while synthesizing products of synthetic and commercial interest. Interestingly, the catalyst was capable of replacing all chlorine atoms in each polychlorinated solvent under the investigations with high conversion. Springer Science+Business Media, LLC 2012.
