mer-[RuCl3(P-P)H2O] (P-P=dppb or diop) as a starting material for the synthesis of binuclear complexes. Crystallographic structures of [(dppb)ClRu-mu(Cl)(3)-RuCl(dppb)] and [(eta(6)-C6H6)Ru-mu(Cl)(3)-RuCl(dppb)]. Imine hydrogenation using mono- and binuclear ruthenium complexes

The reactivity of the mer-[RuCl3(dppb)H2O] complex (1) with di-hydrogen shows that the products formed depend on the conditions of the reaction, i.e., solvents and presence or absence of a base. The new mixed-valence complexes [(diop)ClRu-(h-Cl)(3)-RuCl(dppb)] (3), [(binap)CIRu-(p-Cl)(3)-RuCl(dppb)] (4), [(PPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (6), [(dppn)ClRu-(mu-Cl)(3)-RuCl(dppb)] (7), [(P-ptol(3))(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (8), [(SbPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (9), [(eta(6)-C6H6)Ru-(mu-Cl)(3)-RuCl(dppb)] (11) and the known mixed-valence [(dppb)CIRu-(mu-Cl)(3)-RuCl(dppb)] (5) and [(diop)ClRu-(mu-Cl)(3)-RuCl(diop)] (10) were synthesized from complexes (1) or (2) using a methodology developed in our research group. The known complexes [(dppb)ClRu-(mu-Cl)(2)-RuCl(dppb)] (12), [(dppb)(CO)Ru-(mu-Cl)(3)-RuCl(dppb)] (13) and [H2NEt2][(dppb)ClRu-(mu-Cl)(3)-RuCl(dppb)] (14) were synthesized by changing the reaction conditions between mer-[RuCl3(dppb)H2O] (1) and dihydrogen. The crystal structures of (5) and (11) were determined by single-crystal X-ray diffraction. Some of the complexes described here are effective pre-catalysts for the hydrogenation of imines. Preliminary results on the homogeneous hydrogenation of the imines Ph-CH2-N=CH-Ph and Ph-N=CH-Ph are presented. (C) 2004 Elsevier Ltd. All rights reserved.

1,2-Additionen deprotonierter Alpha-Aminonitrile: Umgepolte Imine als vielseitige Synthesebausteine

Von aromatischen Aldehyden abgeleitete α-Aminonitrile können ohne die Anwendung von Schutzgruppen in α-Position deprotoniert werden, wenn keine lithiumhaltigen Basen verwendet werden. Ziel der vorliegenden Arbeit war es, die Reaktionen deprotonierter α-Aminonitrile mit Elektrophilen zu untersuchen. Die Addition von α-Aminocarbanionen an Imine führt unter intramolekularer Eliminierung von HCN zu Endiaminen, die sich in einer Eintopfsynthese abhängig von der Aufarbeitung in 1,2-Diamine oder 1,2-Diimine umwandeln lassen. Die nach Oxidation durch Luftsauerstoff erhaltenen Diimine können mit dem Reduktionsmittel BH3·THF diastereoselektiv reduziert werden. Es hat sich hier gezeigt, dass durch Zugabe einer katalytischen Menge an NaBH4 hauptsächlich die syn-Diamine erhalten werden, der Zusatz von Phthalsäure wiederum liefert bevorzugt die anti-Produkte. In beiden Fällen wird das Produkt in quantitativer Ausbeute erhalten. So konnte also eine effektive diastereoselektive Reduktionsmethode entwickelt werden, die eine freie Wahl der syn- oder anti-Konfiguration ermöglicht. Um enantiomerenreine 1,2-Diamine zu erhalten, wurden verschiedene Methoden getestet. Sowohl auxiliargesteuerte Synthesen mit einem N-Glycosyl-Aminonitril oder mit chiralen Sulfinyliminen als auch die Reduktion durch chirale Borverbindungen (CBS-Katalysatoren, Triacyloxyborhydrid oder Diisopinocamphenylboran), Transferhydrierungen mit chiralen Difluortitanocen-, Noyori- oder Organophosphat-Katalysatoren sowie enantioselektive Hydrierungen mit chiralen Übergangsmetall-katalysatoren waren jedoch nicht erfolgreich. Die Umsetzung der 1,2-Diimine mit Chlormethylethern oder -estern liefert die entsprechenden unsymmetrischen Imidazoliumsalze. Diese konnten zu N-heterocyclischen Carbenen deprotoniert und erfolgreich als Liganden in Suzuki- und Heck-Reaktionen eingesetzt werden. Durch die 1,2-Addition α-deprotonierter Streckerprodukte und anschließende Reduktion im Eintopfverfahren konnten 1,2-Aminoalkohole in mäßigen bis guten Ausbeuten dargestellt werden. Die Umsetzung von α-Aminocarbanionen mit N-Acyliminen erlaubt zudem die Synthese tetrasubstituierter Imidazole und trisubstituierter Oxazole in drei beziehungsweise vier Stufen: Die zunächst gebildeten α-Amino-α-acylaminopropionitrile können isoliert und in Gegenwart von Base einer Retro-Strecker-Reaktion unterworfen werden. Abhängig vom Substitutionsmuster schließt sich in manchen Fällen nach der Eliminierung von HCN direkt die Cyclisierung zum Imidazol an. Nicht cyclisierte Intermediate lassen sich durch Dehydratisierung mit PCl5 zu Imidazolen umsetzen, aber auch unter sauren Bedingungen zu α-Acylaminoketonen hydrolysieren, welche wiederum durch Einwirkung von PCl5 in Oxazole überführt werden können. Auf diese Weise wurden Imidazole und Oxazole in moderaten bis hohen Gesamtausbeuten hergestellt.

Chiral β-amino alcohols as ligands for the ruthenium-catalyzed asymmetric transfer hydrogenation of N-phosphinyl ketimines

Some chiral β-amino alcohols have been evaluated as potential ligands for the ruthenium-catalyzed asymmetric transfer hydrogenation (ATH) of N-phosphinyl ketimines in isopropyl alcohol. The ruthenium complex prepared from [RuCl2(p-cymene)]2 and (1S,2R)-1-amino-2-indanol has shown to be an efficient catalyst for the ATH of several N-(diphenylphosphinyl)imines, affording the reduction products in very good isolated yields and enantiomeric excesses up to 82%. The inherent rigidity of the indane ring system present in the ligand seems to be very important to achieve good enantioselectivities.

Niobium hydrogenation process Effect of temperature and cooling rate from the hydrogenation temperature

High-purity niobium powder can be produced via the hydrogenation and dehydrogenation processes The present work aimed at the effect of temperature and cooling rate conditions on the niobium hydrogenation process using hydrogen gas The hydrogen contents of the materials were evaluated by weight change and chemical analysis X ray diffraction (XRD) was performed to identify and determine the lattice parameters of the formed hydride phases No hydrogenation took place under isothermal conditions only during cooling of the materials Significant hydrogenation occurred in the 500 C and 700 C experiments leading to the formation of a beta NbH(x) single phase material (C) 2010 Elsevier Ltd All rights reserved

Alternative solvents in carvone hydrogenation

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquimica

Catalytic hydrogenation of carbon dioxide to form methanol and methane

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Effects of prior hydrogenation on the structure and properties of thermally nanocrystallized silicon layers

Nanocrystalline silicon layers have been obtained by thermal annealing of films sputtered in various hydrogen partial pressures. The as-deposited and crystallized films were investigated by infrared, Raman, x-ray diffraction, electron microscopy, and optical absorption techniques. The obtained data show evidence of a close correlation between the microstructure and properties of the processed material, and the hydrogen content in the as-grown deposit. The minimum stress deduced from Raman was found to correspond to the widest band gap and to a maximum hydrogen content in the basic unannealed sample. Such a structure relaxation seems to originate from the so-called "chemical annealing" thought to be due to Si-H2 species, as identified by infrared spectroscopy. The variation of the band gap has been interpreted in terms of the changes in the band tails associated with the disorder which would be induced by stress. Finally, the layers originally deposited with the highest hydrogen pressure show a lowest stress-which does not correlate with the hydrogen content and the optical band gap¿and some texturing. These features are likely related to the presence in these layers of a significant crystalline fraction already before annealing.

Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

Low metal loading catalysts used for the selective hydrogenation of styrene

A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects.

Preparation and characterization oF Ru-Sn/Al2O3 catalysts for the hydrogenation of fatty acid methyl esters

Ru-Sn/Al2O3 catalysts with different Sn loadings were prepared by the coimpregnation method. Several characterization techniques such as TPR, pyridine TPD and catalytic tests for dehydrogenation and hydrogenolysis were used to evaluate and compare such catalysts. TPR results indicate that Sn is deposited both onto the support and as species strongly interacting with Ru. Such non selective deposition modifies the acid and metallic functions of the catalysts. Both total acidity and acid strength distribution are affected: total acidity decreases and new sites of lower acid strength are created. Both dehydrogenating and hydrogenolytic activities are strongly diminished by the addition of Sn. Results of catalytic tests for methyl oleate hydrogenation indicate that methyl stearate is the main product, with only minute amounts of oleyl alcohol produced, and that the addition of Sn diminishes the hydrogenation activity.

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%). The most active prepared catalyst, PdNi(1%), was more selective than the Lindlar catalyst.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.