Direct and Selective Production of Propene from Bio‐Ethanol on Sc‐Loaded In2O3 Catalysts

Propene, one of key building blocks for manufacturing plastics and chemicals, could be directly and stably produced from ethanol in good yields. The conversion degree of ethanol to propene reached approximately 60 mol % by using a 3 atom % scandium‐loaded indium oxide catalyst at 823 K in the presence of water and hydrogen. The introduction of Sc prevented the reduction of In₂O₃ to In metal during the reaction, and that of water decreased the coke formation. Both additions resulted in longer lifetimes of the catalysts. The hydrogen addition increased the conversion of acetone to propene. The reaction pathways are also suggested on the basis of the product distributions and the pulse experiments, ethanol→acetaldehyde→acetone→propene, which is quite different from the shape‐selective catalysis on zeolites and the dimerization‐metathesis of ethene on nickel ion‐loaded silica catalysts.     

Identification, by infra-red spectroscopy, of surface species during propyne hydrogenation

The species retained by a Pd/ZrO₂ catalyst after propyne hydrogenation was investigated by infra-red spectroscopy. The main species identified were a di-sigma adsorbed propene and a sigma/pi adsorbed propyne.     

Defined synthesis of copolymers using metallocene catalysis

The copolymerization of propene with small amounts of ethene, catalyzed by tetrahydroindenyl zirconocenes such as [En(H₄Ind)₂]ZrCl₂ or [Me₂Si(H₄Ind)₂]ZrCl₂ and MAO in liquid propene produces polymers with much higher activities and molecular weights than the homopolymerization of propene. The normal bisindenyl complexes doesn't present such differences. The investigation of the microstructure shows for the tetrahydroindenyl catalyst that after a 2,1-insertion of a propene unit the system is in a sleeping state and can be activated when an ethene unit is inserted. In this case these catalysts become faster than the ansa bis-indenyl catalysts. An active catalyst for the copolymerization of ethene and norbornene is the more temperature stable [Me₃PhPen(Flu)]ZrCl₂. This catalyst produces atactic copolymers with high molecular weights of over 900 000 g/mol at 30°C and 38 mol% of norbornene content.     

Co- and terpolymerizations of ethene and α-olefins with metallocenes

The suitability of the (n-butCp)₂ZrCl₂/methylaluminoxane (MAO) catalyst system for the copolymerization of ethene with propene, hexene, and hexadecene was studied and Ind₂ZrCl₂/MAO was tested as a catalyst for ethene/propene and ethene/hexene copolymerizations. The synergistic effect of longer α-olefin on propene incorporation in ethene/propene/hexene and ethene/propene/hexadecene terpolymerizations was investigated with Et(Ind)₂ZrCl₂MAO and (n-butCp)₂ZrCl₂/MAO catalyst systems. The molar masses, molar mass distributions, melting points, and densities of the products were measured. The incorporation of comonomer in the chain was further studied by segregation fractionation techniques (SFT), by differential scanning calorimetry (DSC), studying the β relaxations by dynamic mechanical analysis (DMA) and by studying the microstructure of some copolymers by ¹³C-NMR. In this study (n-butCp)₂ZrCl₂ and Ind₂ZrCl₂ exhibited equal response in copolymerization of ethene and propene and both catalysts were more active towards propene than longer α-olefins. A nearly identical incorporation of propene in the chain was found for the two catalysts when a higher propene feed was used. A lower hexene feed gave a more homogeneous comonomer distribution curve than a higher hexene feed and also showed the presence of branching. In terpolymerizations catalyzed with (n-butCp)₂ZrCl₂, the hexadecene concentrations of the ethene/propene/hexadecene terpolymers were always very low, and only traces of hexene were detected in ethene/propene/hexene terpolymers. With hexene no clear synergistic effect on the propene incorporation in the terpolymer was detected and with hexadecene the effect of the longer α-olefin was even slightly negative. With an Et(Ind)₂ZrCl₂/MAO catalyst system both hexene and hexadecene were incorporated in the chain in the terpolymerizations. © 1997 John Wiley & Sons, Inc.     

Propene homo- and copolymerization using homogeneous and supported metallocene catalysts based on Me2Si(2-Me-Benz[e]lnd)2ZrCl2

The isoselective propene polymerization using the supported catalyst SiO₂/MAO/Me₂Si(2-Me-Benz[e]Ind)₂ZrCl₂/AlR₃ was investigated and compared with propene polymerization using the corresponding homogeneous catalyst system. The influence of propene concentration, polymerization medium, temperature, comonomer, and external aluminium alkyls on polymerization kinetics and polypropene properties such as molecular mass, stereo- and regioselectivity, morphology, and bulk density was studied. © 1997 John Wiley & Sons, Inc.     

η3-Allylnickel alkoxides and their use as homogeneous and heterogeneous catalysts for the dimerization of olefins

η³-Allylnickel alkoxides {η³-C₃H₅NiOR}₂ (R = Me, Et, i-Pr, Ph, SiPh₃) may be activated by gaseous boron trifluoride (BF₃) to give active catalysts for the dimerization of propene in homogeneous phase. In CH₂Cl₂ at ?20 °C catalytic turnover numbers of 5000 mol propene(mol Ni)^?1h^?1 were measured. The nature of the OR group influences both the catalytic activity and the oligomerization product distribution. The ratio of methylpentenes to dimethylbutenes in the dimer fraction may be controlled by the presence of additional phosphine ligands at the nickel atom. The nickel alkoxide precursor was heterogenized on alumina to give {Al₂O₃}–O–Ni–(η³-C₃H₅). Subsequent activation using gaseous BF₃ generates a powerful heterogeneous olefin dimerization catalyst which converts 50 × 10³ mol propene (mol Ni)^?1 at ?10° to ?5°C in a batchwise process and 143 × 10³ mol propene (mol Ni)^?1 continuously to give 75% dimers and 25% higher oligomers. The solvent-free treatment of oxide supports, e.g. alumina or silica, with gaseous BF₃ produces strong ‘solid acids’. The activated hydroxyl groups on the support surface serve as effective anchor sites for organometallic complexes to form heterogenous catalysts. By reaction of Ni(cod)₂ with {Al₂O₃}O(BF₃)H or {SiO₂}O(BF₃)H, η¹, η²-cyclo-octenylnickel–O fragments may be fixed to the surface. In the absence of halogenated solvents, the resulting catalysts, e.g. {SiO₂}O–(BF₃)–Ni–(η¹, η²-C₈H₁₃), dimerize propene continuously at +5°C at the rate of 800 × 10³ mol liquid propene (mol Ni)^?1.     

Selective catalytic reduction of NO over metal oxide or noble metal-doped In2O3/Al2O3 catalysts by propene in the presence of oxygen

The activities of metal oxide CuO, SnO₂, CoO, Ag₂O, ZnO or noble metal Pt, Pd, Rh-doped In₂O₃/Al₂O₃ catalysts for selective catalytic reduction of NO by propene were investigated. The temperature windows for NO reduction over noble metal-doped In₂O₃/Al₂O₃ catalysts were shifted and broaden slightly compared with single component catalyst alone. This revised version was published online in June 2006 with corrections to the Cover Date.     

Oligomerization of α-olefins by the dimeric nickel bisamido complex [Ni{1-N(PMes2)-2-N(μ-PMes2)C6H4-κN,N′,P,-κP′}]2 activated by methylalumoxane (MAO)

The reaction of Li₂[1,2-{N(PMes₂)}₂C₆H₄], formed in situ from n-BuLi and the corresponding amines, with 1 equiv. of [NiBr₂(DME)] gives [Ni{1-N(PMes₂)-2-N(μ-PMes₂)C₆H₄-κ³N,N′,P-κ¹P′}]₂ (1). After activation by methylalumoxane (MAO), 1 is a highly active catalyst in the oligomerization and isomerization of α-olefins such as ethene, propene, isobutene, 1-hexene and 1,5-hexadiene. For ethene oligomerization turnover frequencies (TOFs) range from 3000 to 79015 h⁻¹, depending on the reaction conditions. The TOF for propene oligomerization reaches 1 190 730 h⁻¹. To our knowledge, catalyst 1, activated by MAO, is the most active catalyst for the oligomerization of propene and outperforms the best known complexes for this reaction. In the reactions with 1-hexene, 1,5-hexadiene and isobutene dimerization and isomerization products were observed.     

Silane‐bridged diphosphine ligand for palladium‐catalyzed ethylene oligomerization

In this study, bis(diphenylphosphinemethyl)dimethyl silane ( L1 ) and its palladium(II) halide complex, L1 /PdCl₂ ( C1 ), were synthesized and characterized. Single‐crystal X‐ray analysis of the complex revealed bidentate coordination at the Pd center. In combination with methylaluminoxane (MAO) as co‐catalyst, C1 exhibited excellent catalytic activity and selectivity for ethylene dimerization toward butene. The maximum catalytic activity obtained from the C1 /MAO system for ethylene dimerization to yield butenes was 7.33 × 10⁵ g/(mol_Pd · h). The selectivity toward butene remained stable and high (> 96%) over the various conditions.     

Kinetics and mechanism of the wet oxidation of propene to acetone in the presence of Pd2+ ions and Mo-V-phosphoric heteropoly acids ?

Summary Oxidation of propene to acetone in water solutions in the presence of homogeneous catalysts (Pd²⁺ + HPA-x, where HPA-x = H_3+xPV_xMo_12-xO₄₀, x = 1-4) is studied. This reaction is shown to be of the 1st order with respect to C₃H₆ and of the 0.5th order with respect to Pd. The reaction rate does not depend on the concentration of HPA-x and acidity of the catalyst solution. The apparent activation energy of the reaction is 21 kJ/mol. A reaction mechanism is proposed.     

Dimerization and Oligomerization of Ethylene Catalyzed by a Palladium(II) Complex with Imine‐phosphine Ligand

The palladium‐iminophosphine complex [Pd(P‐N)(CH₃)Cl] (P‐N = o‐diphenyl‐phosphino‐N‐benzaldimine) has been found to be a catalyst for dimerization and trimerization of ethylene. Some mechanistic insight concerning this oligomerization is discussed.     

Copolymerization of propene with high-1-olefin using a MgCl2/TiCl4 catalyst

Copolymerization of propene and 1-olefins including 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene were studied with the catalyst system MgCl₂/TiCl₄-Al(i-Bu)₃. It was found that the polymerization productivity and the consumption rate of propene are improved significantly in the presence of the comonomer. The total productivity of propene/1-olefin copolymerizations decreases as follows: 1-octene> 1-decene>1-dodecene>1-hexadecene>1-tetradecene. The reactivity ratios were estimated from the copolymerization results. ¹³C NMR was used to characterize the microstructures of propene/1-octene copolymer. Finally, the oxygen enrichment behavior of propene/1-octene copolymer was investigated.     

Oxidative coupling of alkynes mediated by nitroxyl radicals under Sonogashira conditions and Pd-free catalytic approach to stable radicals of 3-imidazoline family with triple bonds

In the presence of Pd catalyst, 3-imidazoline nitroxyl radicals promote oxidative coupling (dimerization) of terminal alkynes even in the absence of Cu(II) additives. On the other hand, the Pd-free CuI-PPh₃-K₂CO₃-DMF catalytic system leads to the efficient cross-coupling of 1-hydroxy-4-[2-(p-iodophenyl)vinyl]-2,2,5,5-tetramethyl-3-imidazoline-3-oxide with terminal aryl- and hetarylacetylenes with the formation of 4-[2-(aryl/hetarylethynyl)phenyl)vinyl]-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyls in 70-75% yields.     

Formation of palladium nanoparticles in olefin oxidation with iron(III) aqua ions in the presence of the Pd/ZrO2/SO4 metallic catalyst

The reactions of the Pd/ZrO₂/SO₄-catalyzed oxidation of ethylene, propene, and but-1-ene in a 0.1–1.5 M solution of perchloric acid with iron(III) aqua ions to carbonyl compounds, viz., acetaldehyde, acetone, and methyl ethyl ketone, respectively, were studied. The formation of palladium nanoparticles (5 nm) in solution on contact of the initial heterogeneous Pd/ZrO₂/SO₄ catalyst with perchloric acid was proved by transmission electron microscopy. The palladium nanoparticles are assumed to play the key role in olefin oxidation with the iron(III) aqua ions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 627–632, April, 2006.     

Sulfinate as cocatalyst 3 : Palladium catalyzed dimerization of butadiene with acylamino ketones

A catalyst generated in situ from PdCl₂ (1 mole) and p-CH₃C₆H₄SO₂-Na·4H₂O (5 mole) promotes the dimerization of butadiene with the incorporation of α-acylamino ketones (1a～1h) to provide α-acylamino α-(2,7-octadienyl) ketones (2a～2h) in good yields. This new type of C-C bond forming reaction is not effected by the catalyst of Pd(PPh₃)₄ except for one example (with 1e).     

Structural Aspects of Palladium and Platinum Complexes With Chiral Diphosphinoferrocenes Relevant to the Regio‐ and Stereoselective Copolymerization of CO with Propene

A series of chiral diphosphinoferrocene ligands 3a – i , derived from josiphos (=(2R)‐1‐[(1R)‐1‐(dicyclohexylphosphino)ethyl]‐2‐(diphenylphosphino)ferrocene, formerly called {(R)‐1‐[(S)‐2‐(diphenylphosphino)ferrocenyl]ethyl}dicycloxexylphosphine) where the electronic properties of the ligand are systematically varied, were prepared. X‐Ray studies of five of these new ligands confirmed that these compounds display very similar conformations in the solid state and that no structural criteria could be found indicating the modified electronic properties. These ligands find application in the Pd‐catalyzed highly regio‐ and stereoselective CO/propene copolymerization reaction, where the electronic properties of the ligand show a great impact on the catalyst activity. Coordination‐chemical aspects of these diphosphinoferrocenes relevant to the CO/propene copolymerization reaction were addressed by the preparation and characterization of Pd‐ and Pt‐complexes of the general formula [PdCl₂(P−P)] ( 5 ), [PdMe₂(P−P)] ( 6 ), [PdClMe(P−P)] ( 7 ), [PdMe(MeCN)(P−P)]PF₆ ( 8 ), and [PtClMe(P−P)] ( 9 ) (P−P=chiral diphosphinoferrocene ligand ( 3a – h ), four of which were characterized by X‐ray crystallography.     

Propene polymerization using homogeneous MAO-activated metallocene catalysts: Me2Si(Benz[e]Indenyl)2ZrCl2/MAO vs. Me2Si(2-Me-Benz[e]Indenyl)2ZrCl2/MAO

Propene was polymerized at 40°C and 2-bar propene in toluene using methylalumoxane (MAO) activated rac-Me₂Si(Benz[e]Indenyl)₂ZrCl₂ ( BI ) and rac-Me₂Si(2-Me-Benz[e]Indenyl)₂ZrCl₂ ( MBI ). Catalyst BI /MAO polymerizes propene with high activity to afford low molecular weight polypropylene, whereas MBI /MAO is less active and produces high molecular weight polypropylene. Variation of reaction conditions such as propene concentration, temperature, concentration of catalyst components, and addition of hydrogen reveals that the lower molecular weight polypropylene produced with BI /MAO results from chain transfer to propene monomer following a 2,1-insertion. A large fraction of both metallocene catalyst systems is deactivated upon 2,1-insertion. Such dormant sites can be reactivated by H₂-addition, which affords active metallocene hydrides. This effect of H₂-addition is reflected by a decreasing content of head-to-head enchainment and the formation of polypropylene with n-butyl end groups. Both catalysts show a strong dependence of activity on propene concentration that indicates a formal reaction order of 1.7 with respect to propene. MBI /MAO shows a much higher dependence of the activity on temperature than BI /MAO. At elevated temperatures, MBI /MAO polymerizes propene faster than BI /MAO. © 1995 John Wiley & Sons, Inc.     

Role of CO2 in dehydrogenation of propane over CrOX/SiO2 catalyst with low Cr content

When ethene alone was contacted with silica supported cobalt catalyst (Co/SiO₂), ethene homologation took place with considerable activity. Moreover, the propene metathesis reaction was suppressed ca. 1/6 fold as much as in the case using MoO_X/SiO₂ catalyst. The possibility of selective homologation with a lower activity for metathesis was suggested for the cobalt-based catalyst system.     

Reduction of nitrate ion using hydrogen permeating Pd foil electrodes

The successive electrochemical reduction system using hydrogen-permeable Pd foil electrodes with Pd black catalyst was applied to reduction of nitrate ion. It was revealed that the second metals co-deposited to Pd black catalyst showed an excellent selectivity for decomposition of NO ₃ ⁻ to N₂, and was stable for at least 200 days. This system employing a compact and a simple electrolysis cell is expected to be an alternative or a supplement to conventional biological treatments for nitrate removal.     

Selective Hydrogenation of Citral over a Carbon‐titania Composite Supported Palladium Catalyst

A novel carbon‐titania composite material, C/TiO₂, has been prepared by growing carbon nanofibers (CNFs) on TiO₂ surface via methane decomposition using Ni‐Cu as a catalyst. The C/TiO₂ was used for preparing supported palladium catalyst, Pd/C/TiO₂. The support and Pd/C/TiO₂ catalyst were characterized by BET, SEM, XRD and TG‐DTG. Its catalytic performance was evaluated in selective hydrogenation of citral to citronellal, and compared with that of activated carbon supported Pd catalyst. It was found that the Pd/C/TiO₂ catalyst contains 97% of mesopores. And it exhibited 88% of selectivity to citronellal at citral conversion of 90% in citral hydrogenation, which was much higher than that of activated carbon supported Pd catalyst. This result may be attributed to elimination of internal diffusion limitations, which were significant in activated carbon supported Pd catalyst, due to its microporous structure.