Double bond migration and racemization during the hydrogenation of olefins

Huntsman, William D.; Madison, Norman L.; Schlesinger, Sheldon I.

doi:10.1016/0021-9517(63)90005-8

Cited by 16 publications

(5 citation statements)

References 21 publications

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“…Analysis of literature data concerning isomerization of double bond in unsaturated hydrocarbons and alcohols showed that supported noble metals provide sufficient selectivity in this process [4,7,[15][16][17]. However, experiments carried out with isoprenol in the range of 75-90 8C in the stream of H 2 on silica supported Pd, Pt, Ru and Ir catalysts led to the preferred hydrogenation of double bond.…”

Section: Resultsmentioning

confidence: 85%

Liquid phase isomerization of isoprenol into prenol in hydrogen environment

Kogan

Kaliya

Froumin

2006

Applied Catalysis A: General

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Section: Resultsmentioning

confidence: 85%

Liquid phase isomerization of isoprenol into prenol in hydrogen environment

Kogan

Kaliya

Froumin

2006

Applied Catalysis A: General

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“…Amines also play an important role in modifying the selectivity and activity of other catalytic reactions. For example, palladium [20] and ruthenium [21] based hydrogenation catalysts are enhanced by amine modification and the enantioselective hydrogenation of a-functionalised ketones and olefins over platinum [22] requires a modifier containing a basic nitrogen atom [23][24][25][26] and the presence of oxygen [27].…”

Section: Introductionmentioning

confidence: 99%

Molecularly Resolved Studies of the Reaction of Pyridine and Dimethylamine with Oxygen at a Cu(110) Surface

et al. 2005

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Pyridine and dimethylamine have been studied at clean and oxidised Cu(110) surfaces as model systems for the interaction of amines with heterogeneous catalysts using scanning tunnelling microscopy and X-ray photoelectron spectroscopy. Both molecules interact strongly with sub monolayer concentrations of chemisorbed oxygen causing a change from the well known p(2 · 1)O(a) islands to a (3 · 1) structure. XPS shows a 1:1 correspondence between the concentration of surface oxygen and that of chemisorbed pyridine but the stoichiometry of the dimethylamine/oxygen system could not be directly measured because of a slow reaction which results in the desorption of oxygen as water and the formation of a chemisorbed amide. The amide also decomposes at room temperature and desorbs leaving a clean surface. However, the 2:1 stoichiometry of the dimethylamine/oxygen reaction suggests a 1:1 dimethylamine:oxygen ratio in the (3 · 1) structure. The results of the study are interpreted in terms of an amineoxygen complex, which may provide a general model for the interaction of amines with oxygen at metal surfaces.

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“…Amines have applications in many interface related areas including corrosion inhibition, − adhesion, − and heterogeneous catalysis. , In the latter case, amines are commonly used not only as reactants but also as catalyst modifiers. − Pfaltz, for example, has shown that a basic nitrogen group is a necessary component of chiral modifiers for the hydrogenation of α-functionalized ketones. − The interaction of the amine functionality with the surface is therefore a subject of some importance in surface science. Our own interest in amine surface chemistry stems from studies of ammonia oxidation − and of the interaction of pyridine with surface oxygen, where intermolecular complexes between pyridine and both molecular oxygen transients and chemisorbed atomic oxygen , have been demonstrated.…”

Section: Introductionmentioning

confidence: 99%

STM and XPS Studies of the Oxidation of Aniline at Cu(110) Surfaces

2004

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Aniline chemisorption at clean and partially oxidized Cu(110) surfaces at 293 K is compared with the reaction of a 300:1 aniline/dioxygen mixture at the same surface using STM and XPS. Limited dissociation occurs at the clean surface but in the presence of chemisorbed oxygen efficient oxy-dehydrogenation takes place with water desorption and the formation of chemisorbed phenyl imide (C6H5N(a)) with a reaction stoichiometry that changes with coverage. The adsorption site of the phenyl group is identified by STM to be the 2-fold hollow and it is proposed that the nitrogen is situated over the short bridge site. Chemisorptive replacement of oxygen gives a maximum phenyl imide concentration of 2.8 × 1014 molecules cm-2 at which coverage the surface is dominated by a mixture of three ordered domains with structures described by , , and unit meshes. Adsorption of aniline and dioxygen mixtures however results in phenyl imide concentrations up to 3.4 × 1014 cm-2 molecules cm-2 and a highly ordered biphasic structure characterized by and domains. A discrepancy between the concentrations measured by XPS and those calculated from the STM structures is discussed in terms of π-stacking of the phenyl rings in the adsorbed monolayer. Finally the chemistry of aniline is compared with that of ammonia and the importance of the NH bond strength and the basicity of the amine discussed.

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Double bond migration and racemization during the hydrogenation of olefins

Cited by 16 publications

References 21 publications

Liquid phase isomerization of isoprenol into prenol in hydrogen environment

Liquid phase isomerization of isoprenol into prenol in hydrogen environment

Molecularly Resolved Studies of the Reaction of Pyridine and Dimethylamine with Oxygen at a Cu(110) Surface

STM and XPS Studies of the Oxidation of Aniline at Cu(110) Surfaces

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