Hydrogenation of various organic substrates using polystyrene anchored orthometallated ruthenium (II) complex as catalyst

The catalytic activity of orthometallated complex [Ru(azb)(CO)₂Cl]₂ (Hazb = azobenzene) anchored to macroporous polystyrene beads was investigated towards the reduction of organic nitrocompounds, alkenes, alkynes, nitriles, Schiff bases, ketones and aldehydes under high pressure, high temperature conditions in mild coordinating media. Comparative studies have been done with the corresponding unsupported metal complexes. The polymer catalyst was found to be comparable to its homogeneous counterpart in activity and product selectivity but superior in stability and reusability. A tentative reduction mechanism was proposed on the basis of kinetic studies and the isolation of reactive intermediates.     

Hydrogenation of biological membranes using a polymer-anchored colloidal palladium catalyst

Colloidal palladium anchored onto the surface of insoluble polyvinyl-polypirrolidone (Pd-PVPP) is anactive, non-permeable catalyst for surface selective hydrogenation of model or isolated biomembranes.

---

, , , .

     

Hydrogenation of heterocyclic analogs of β-nitrostyrene over palladium catalyst

A study is made of the liquid phase hydrogenation of-(-furyl)-and-(-thienyl)--nitroethylenes over Pd black. It is shown that the nature of the substituent (phenyl, furyl, thienyl) does not affect the mode of addition of the hydrogen to the nitrovinyl group. Conditions are found for catalytic synthesis of high yields of heterylacetaldehyde oximes from nitroalkenes.     

A highly regioselective hydrophosphination of terminal alkynes with tetraphenyldiphosphine in the presence of palladium catalyst

A novel palladium-catalyzed hydrophosphination of alkynes with tetraphenyldiphosphine takes place regioselectively to provide vinylic phosphines, which undergo air-oxidation during workups, affording the corresponding vinylphosphine oxides in good yields.     

Reduction of alkynes into 1,2-dideuterioalkenes with hexamethyldisilane and deuterium oxide in the presence of a palladium catalyst

A combination of hexamethyldisilane and deuterium oxide was found to work as a deuterium transfer reagent for alkynes in the presence of a catalytic amount of a palladium complex to give (E)-1,2-dideuterioalkenes selectively through the corresponding (Z)-isomer.     

Hydrogenation of 1-alkenes catalysed by anchored montmorillonite palladium(II) complexes: a kinetic study

Hydrogenation of 1-hexene, 1-heptene and 1-octene was carried out using anchored montmorillonitebipyridinepalladium(II) acetate (C_I), montmorillonitebipyridinepalladium(II) chloride (C_II) and montmorillonitediphenylphosphinopalladium(II) chloride (C_III) in THF. Under the reaction conditions 100% saturation of the carbon–carbon double bond was observed. The observed rates were first order with respect to the partial pressure of hydrogen and fractional order with respect to [substrate] and [catalyst]. The hydrogenation rates were found to be: 1-hexene > 1-heptene > 1-octene for all three catalysts. The reactivity order of various catalysts is: C_I > C_II > C_III. Thermodynamic and activation parameters were evaluated. A rate law and a plausible mechanism has been proposed.     

Hydrogenation of substituted nitroarenes by a polymer-bound palladium(II) Schiff base catalyst

The catalytic activity of a polymer-bound palladium Schiff base catalyst was investigated toward the reduction of aryl nitro compounds under ambient temperature and pressure. The dependence of the rate of hydrogenation of o-nitroaniline and o-nitrotoluene on substrate concentration, catalyst concentration and temperature has been determined. Based on the results obtained a plausible mechanism for the hydrogenation reaction is proposed and a rate expression is deduced. The energy and entropy of activation have been evaluated from the kinetic data. The polymer-bound catalyst was found to be better than its homogeneous analog PdCl₂(NSBA) [NSBA = N-salicylidene benzylamine] for both stability and reusability. Recycling studies revealed that the catalyst could be used six times without metal leaching or significant loss in activity.     

Silylstannation of terminal alkynes using a recyclable palladium(0) catalyst immobilised in an ionic liquid

Silylstannanes can be regioselectively added across terminal alkynes in a quantitative fashion in the presence of a palladium(0) catalyst immobilised in the [bmim]PF6 ionic liquid which can be recycled without loss of activity.     

Synthesis of isotactic polystyrene with a rare-earth catalyst

Polymerization of styrene with the neodymium phosphonate Nd(P₅₀₇)/H₂O/Al(i-Bu)₃ catalytic system has been examined. The polymer obtained was separated into a soluble and an insoluble fraction by 2-butanone extraction. ¹³C-NMR spectra indicate that the insoluble fraction is isotactic polystyrene and the soluble one is syndiotactic-rich atactic polystyrene. The polymerization features are described and discussed. The optimum conditions for the polymerization are as follows: [Nd] = (3.5–5.0) × 10⁻² mol/L; [styrene] = 5 mol/L; [Al]/[Nd] = 6–8 mol/mol; [H₂O]/[Al] = 0.05–0.08 mol/mol; polymerization temperature around 70°C. The percent yield of isotactic polystyrene (IY) is markedly affected by catalyst aging temperature. With increase of the aging temperature from 40 to 70°C, IY increases from 9% to 48%. Using AlEt₃ and Al(i-Bu)₂H instead of Al(i-Bu)₃ decreases the yield of isotactic polystyrene. Different neodymium compounds give the following activity order: Nd(P₅₀₇)₃ > Nd(P₂₀₄)₃ > Nd(OPrⁱ)₃ > NdCl₃ + C₂H₅OH > Nd(naph)₃. With Nd(naph)₃ as catalyst, only atactic polystyrene is obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1773–1778, 1998     

Sonogashira reaction of aryl and heteroaryl halides with terminal alkynes catalyzed by a highly efficient and recyclable nanosized MCM-41 anchored palladium bipyridyl complex

A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.     

Phase transfer catalysts anchored to polystyrene

Quarternary phosphonium and ammonium salts attached to polystyrene resins by short (2 - 3 atom) carbon chains are highly active phase transfer catalysts for a variety of nucleophilic substitution reactions.     

Copolymerization of carbon monoxide and norbornadiene with a palladium catalyst

Carbon monoxide (CO) and norbornadiene (NBD) with Pd(CH₃CN)₄(BF₄)₂ were copolymerized under various conditions at 50°C. Elemental analysis, infrared spectra, UV, Raman, and NMR spectra showed that the copolymers contained both ketone and unsaturated ring structures. Bidentate nitrogen ligands and phosphorus ligands proved to be more effective at stabilizing catalytic activity than monodentate arsenic ligands or phosphorus ligands. Methanol, protic acid, and an oxidant served as the coinitiator and chain transfer agent, respectively. X-ray diffraction analysis showed the copolymer to be partially crystalline. Thermogravimetric analysis showed that the TG curve for the NBD/CO copolymer has two stages with two maxima peaks at 251 and 470°C. This phenomenon was probably due to increased instability of the copolymers as CO content is increased. Hydrogenation of norbornadiene/CO copolymer with LiAlH₄ and Pd/C in THF yields a hydroxyl-containing polymer and norbornene/CO copolymer, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1157–1166, 1997     

Sequential asymmetric homoallenylation of primary amines with a palladium catalyst

Optically active bis(homoallenyl)amines bearing two chiral axes with the same sense of axial chirality were prepared by a one-pot, palladium-catalyzed sequential homoallenylation of primary amines with 2,3-allenyl phosphates.     

Covalently anchored lipid structures on amine-enriched polystyrene

The study of the adhesion of lipid vesicles on surfaces is of increasing interest in the field of medical implants and tissue engineering (protein-resistant surfaces), drug delivery, biosensors, and biochips. In this work, lipid coverage was developed from PEG-coated vesicles (with sizes from 100 to 300 nm) by covalently binding poly(ethylene glycol)-alpha-disteroylphosphatidylethanolamine-omega-benzotriazole carbonate (DSPE-PEG-BTC) molecules onto the surface amine groups by carbamate chemistry. Lipid surface density and the surface structure of multilamellar (MLVs) and extruded unilamellar (LUVs) vesicles deposited on three types of polystyrene (PS) well-plates were probed by fluorescence and atomic force microscopy (AFM) imaging. A significant difference in the vesicle surface coverage of PS substrates was observed with a substantial increase in lipid multilayers on the amine-enriched PS surface using both unilamellar and multilamellar vesicles.     

Hydrogenolysis of difurylethane on a palladium catalyst

Chemistry of Heterocyclic Compounds -