Selective Hydrogenation of 1,3‐Butadiene to 1‐Butene by Pd(0) Nanoparticles Embedded in Imidazolium Ionic Liquids

The reduction of Pd(acac)₂ (acac=acetylacetonate), dissolved in 1‐n‐butyl‐3‐methylimidazolium hexafluorophosphate (BMI⋅PF₆) or tetrafluoroborate (BMI⋅BF₄) ionic liquids, by molecular hydrogen (4 atm) at 75 °C affords stable, nanoscale Pd(0) particles with sizes of 4.9±0.8 nm. Inasmuch as 1,3‐butadiene is at least four times more soluble in the BMI⋅BF₄ than butenes, the selective partial hydrogenation could be performed by Pd(0) nanoparticles embedded in the ionic liquid. Thus, the isolated nanoparticles promote the hydrogenation of 1,3‐butadiene to butenes under solventless or multiphase conditions. Selectivities up to 97% in butenes were observed in the hydrogenation of 1,3‐butadiene by Pd(0) nanoparticles embedded in BMI⋅BF₄ under mild reaction conditions (40 °C and 4 atm of hydrogen at constant pressure). Selectivities up to 72% in 1‐butene were achieved at 99% 1,3‐butadiene conversion, 40 °C and 4 atm of constant pressure of hydrogen. The amounts of butane (fully hydrogenated 1,3‐butadiene) and cis‐2‐butene products are marginal and the butenes do not undergo isomerisation process, indicating that the soluble Pd(0) nanoparticles possess a pronounced surface‐like rather than homogeneous‐like catalytic properties.     

γ‐Alumina supported Cu‐Ni bimetallic catalysts: Characterization and selective hydrogenation of 1,3‐butadiene

Addition of a second metal often improves the selectivity of a supported catalyst for the hydrogenation of 1,3‐butadiene. Catalysts containing 15 wt% Ni and varying amounts of Cu were prepared and characterized by TPR, XRD and XPS. The Cu‐Ni interaction affects the reduction behavior of the catalysts. TPR result shows that the synergetic effect of copper and nickel modifies the capability of metal to combine with hydrogen in bulk phase. The Ni 2p spectra in XPS shows significant shifts toward lower binding energies with increasing copper loading. From XRD results it is represented that aggregation of nickel occurs more easily due to the copper addition. The adding of copper on Ni/Al₂O₃ makes the conversion rate decreased and increases the selectivity to 1‐butene.     

Comparison of homogeneous and heterogeneous palladium hydrogenation catalysts

Mechanistic and kinetic studies of Pd-catalyzed hydrogenation at atmospheric pressure and 30–100 C were carried out with methyl sorbate, methyl linoleate and conjugated linoleate. Homogeneous Pd catalysts and particularly Pd-acetylacetonate [Pd(acac)₂] were significantly more selective than Pd/C in the hydrogenation of sorbate to hexanoates, mainlytrans-2-hexenoate. Relative rate constants for the different parallel and consecutive reactions, determined by computer simulation, indicated that the low diene selectivity of Pd/C can be dattributed to a significant direct reduction of sorbate to hexanoate. The similar behavior of PdCl₂ to that of Pd/C suggests that Pd(II) was initially reduced to Pd(O). Valence stabilization of PbCl₂ by adding DMF or a mixture of Ph₃P and SnCl₂ increased the diene selectivity but decreased the activity. Stabilization of Pd(acac)₂ with triethylaluminum (Ziegler catalyst) resulted in increased activity but decreased selectivity. The kinetics of methyl linoleate hydrogenation showed that although Pd(acac)₂ was only half as active as Pd/C, their respective diene selectivity was similar (10.4 and 9.6). The much greater reactivity of conjugated compared with unconjugated linoleate toward Pd(acac)₂ suggests the possible formation of conjugated dienes as intermediates that are rapidly reduced and not detected in the lipid phase during hydrogenation.     

Solid Catalyst with Ionic Liquid Layer (SCILL) – A New Concept to Improve Selectivity Illustrated by Hydrogenation of Cyclooctadiene

A new concept of a solid catalyst with ionic liquid layer (SCILL) as a novel method to improve the selectivity of heterogeneous catalysts is presented. The sequential hydrogenation of cyclooctadiene (COD) to cyclooctene (COE) and cyclooctane on a commercial Ni catalyst coated with the ionic liquid [BMIM][n‐C₈H₁₇OSO₃] was tested as first model system. Compared to the original catalyst, the coating of the internal surface with the ionic liquid (IL) strongly enhances the maximum intrinsic COE yield from 40 to 70 %. This effect is already achieved for a pore filling degree of only 10 % and cannot be explained by pore diffusion, as shown by experiments with different particle sizes and theoretical considerations. The IL layer is very robust and no leaching into the organic phase was detectable.     

The influence of the structural and electronic characteristics of palladium on the activity and selectivity of Pd/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd-Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for the hydrogenation of acetylene hydrocarbons

The influence of the structural and electronic characteristics of nonpromoted and cobalt-promoted Pd catalysts on their adsorption and catalytic properties is studied. It is shown that the conversion of vinylacetylene depends on the dispersion of palladium for both types of catalysts synthesized from acetate and acetylacetonate complexes. The palladium acetylacetonate catalysts have a higher palladium dispersion than the samples obtained from acetate complex solutions, thus leading to a higher conversion of vinylacetylene. It is established that the selectivity of vinylacetylene conversion into 1,3-butadiene on palladium acetate and acetylacetonate catalysts depends on the state of the 3d orbitals of surface Pd atoms. The palladium acetate catalysts are characterized by a higher electron density on the 3d orbital in comparison with the acetylacetonate samples, thus producing higher selectivities of vinylacetylene conversion into 1,3-butadiene. The introduction of cobalt into Pd/δ-Al₂O₃ catalyst synthesized from acetylacetonate complex leads to the formation of bimetallic Pd-Co particles, in which Pd atoms have higher electron density than those in the nonpromoted Pd/δ-Al₂O₃ catalyst, due probably to the donation of electron density from promoter atoms, with a resulting decline in the adsorption ability of bimetallic particles with regard to 1,3-butadiene and hydrogen. As a consequence, the selectivity of vinylacetylene conversion into 1,3-butadiene increases. Requirements for the size, dispersion, and electronic characteristics of the active component in the catalysts for the selective hydrogenation of vinylacetylene are formulated, and two techniques for their synthesis are proposed.     

Liquid‐Phase Catalytic Hydrogenation of p‐Chlorobenzophenone to p‐Chlorobenzhydrol over a 5 % Pd/C Catalyst

The kinetics of the liquid‐phase catalytic hydrogenation of p‐chlorobenzophenone have been investigated over a 5 % Pd/C catalyst. The effects of hydrogen partial pressure (800–2200 kPa), catalyst loading (0.4–1.6 gm dm^–3), p‐chlorobenzophenone concentration (0.37–1.5 mol dm^–3), and temperature (303–313 K) were studied. A stirring speed > 20 rps has no effect on the initial rate of reaction. Effects of various catalysts (Pd/C, Pd/BaSO₄, Pd/CaCO₃, Pt/C, Raney nickel) and solvents (2‐propanol, methanol, dimethylformamide, toluene, xylene, hexane) on the hydrogenation of p‐chlorobenzophenone were also investigated. The reaction was found to be first order with respect to hydrogen partial pressure and catalyst loading, and zero order with respect to p‐chlorobenzophenone concentration. Several Langmuir‐Hinshelwood type models were considered and the experimental data fitted to a model involving reaction between adsorbed p‐chlorobenzophenone and hydrogen in the liquid phase.     

Hydrogenation of 2-Butyn-1,4-diol in the Presence of Functional Crosslinked Resin Supported Pd Catalyst. The Role of Polymer Properties in Activity/Selectivity Pattern

Functional gel type resins of various crosslinking degrees (3–20%) with C=O and carboxylic groups were used as the supports for Pd catalysts (0.5–2 wt% Pd). The role of polymer properties was studied in the hydrogenation of 2-Butyne-1,4-diol (B3-D) to alkene (B2-D) and alkane (B1-D). Hydrogenation was studied at atmospheric pressure of hydrogen using THF, H₂O and THF + H₂O mixtures as the solvents. Systematic studies were carried out to determine the role of the type of solvent, crosslinking degree of polymer, the content of Pd in catalysts, initial B3-D concentration and the procedure of catalyst reduction in activity/selectivity behaviour of catalysts. Swelling degree of polymer matrix under the catalytic run exhibits crucial role in the activity and selectivity to alkene, B2-D. In the presence of highly expanded catalyst (THF solvent, 3% crosslinking degree, 1 wt% Pd) the alkyne, B3-D, is hydrogenated to alkene, B2-D, with selectivity ca. 85% up to high B3-D conversion (90%). The suppression of alkene to alkane hydrogenation in the stage of B3-D is ascribed to high ability of Pd centres in the Pd/OFP catalysts to strong adsorption of alkyne substrate. It may also be related to steric hindrances of polymer in the vicinity of active Pd centres. At small content of added water (5% by vol.) to THF the catalysts offer very attractive performance in terms of activity and 98% selectivity to alkene. Water facilitates interactions of B3-D with functional groups of polymer that leads to better expansion of polymer matrix and more effective suppression of alkene hydrogenation in the alkyne stage.     

Kinetics of hydrogenation of 4‐chloro‐2‐nitrophenol catalyzed by Pt/carbon catalyst

Hydrogenation of 4‐chloro‐2‐nitrophenol (CNP) was carried out at moderate hydrogen pressures, 7–28 atm, and temperatures in the range 298–313 K using Pt/carbon and Pd/γ‐Al₂O₃ as catalysts in a stirred pressure reactor. Hydrogenation of CNP under the above conditions gave 4‐chloro‐2‐aminophenol (CAP). Dechlorination to form 2‐aminophenol and 2‐nitrophenol is observed when hydrogenation of CNP is carried out above 338 K, particularly with Pd/γ‐Al₂O₃ catalyst. Among the catalysts tested, 1%Pt/C was found to be an effective catalyst for the hydrogenation of CNP to form CAP, exclusively. To confirm the absence of gas–liquid mass transfer effects on the reaction, the effect of stirring speed (200–1000 rpm) and catalyst loading (0.02–0.16 g) on the initial reaction rate at maximum temperature 310 K and substrate concentration (0.25 mole) were thoroughly studied. The kinetics of hydrogenation of CNP carried out using 1%Pt/C indicated that the initial rates of hydrogenation had first order dependence with respect to substrate, catalyst and hydrogen pressure in the range of concentrations varied. From the Arrhenius plot of ln rate vs 1000/T, an apparent activation energy of 22 kJ mol^?1 was estimated. © 2001 Society of Chemical Industry     

Hydrogenation of methyl sorbate and soybean esters with polymer-bound metal catalysts

New polymer-bound hydrogenation catalysts were made by complexing PdCl₂, RhCl₃·3H₂O, or NiCl₂ with anthranilic acid anchored to chloromethylated polystyrene. The Pd(II) and Ni(II) polymers were reduced to the corresponding Pd(O) and Ni(O) catalysts with NaBH₄. In the hydrogenation of methyl sorbate, these polymer catalysts were highly selective for the formation of methyl 2-hexenoate. The diene to monoene selectivity decreased in the order: Pd(II), Pd(O), Rh(I), Ni(II), Ni(O). Kinetic studies support 1,2-reduction of the Δ4 double bond of sorbate as the main path of hydrogenation. In the hydrogenation of soybean esters, the Pd(II) polymer catalysts proved superior because they were more active than the Ni(II) polymers and produced lesstrans unsaturation than the Rh(I) polymers. Hydrogenation with Pd(II) polymers at 50~100 C and 50 to 100 psi H₂ decreased the linolenate content below 3% and increasedtrans unsaturation to 10~26%. The linolenate to linoleate selectivity ranged from 1.6 to 3.2. Reaction parameters were analyzed statistically to optimize hydrogenation. Recycling through 2 or 3 hydrogenations of soybean esters was demonstrated with the Pd(II) polymers. In comparison with commercial Pd-on-alumina, the Pd(II) polymers were less active and as selective in the hydrogenation of soybean esters but more selective in the hydrogenation of methyl sorbate. Presented at ISF-AOCS Meeting, New York, April 1980.     

Competitive Hydrogenation of Alkyl‐Substituted Arenes by Transition‐Metal Nanoparticles: Correlation with the Alkyl‐Steric Effect

The influence of substituents on rate constants of the hydrogenation of monoalkylbenzenes by transition metal nanoparticles or by classical heterogeneous catalysts can be rationalized in terms of the Taft rule. A series of the initial reaction rate constants obtained from various competitive toluene/benzene and toluene/monoalkylbenzene hydrogenation experiments catalyzed by transition‐metal nanoparticles prepared in the presence of imidazolium ionic liquids or surfactants [Ir(0), Rh(0) and Ru(0)] or by classical heterogeneous catalysts (PtO₂, Rh/C, Rh/Al₂O₃, Ru/C, Ru/Al₂O₃ and Pd/C) have been correlated with the Taft equation . Satisfactory correlation coefficients (r) (between 0.96 and 0.99) and positive slopes (ρ) between 0.38 and 0.83 have been obtained. The results clearly show that the reaction constants for the alkyl‐substituents can be expressed by steric factors and are independent of any other non‐steric factors. It is suggested that bulky alkylbenzene substituents, for both transition metal nanoparticles and classical heterogeneous hydrogenation reactions, lower the overall hydrogenation rate, implying a more disturbed transition state compared to the initial state of the hydrogenation (in terms of the Horiuti–Polanyi mechanism). This competitive method is suitable for the estimation of the constant selectivity for couples of alkylbenzenes in which the difference in hydrogenation rates are very high and experimentally difficult to measure and also useful for the design of more selective “nano” and classical catalysts for hydrogenation reactions.     

The choice of an optimal composition and preparation method of non-promoted Pd/Al2O3 and promoted Pd-Co/Al2O3 catalysts for the selective hydrogenation of vinylacetylene

For the purpose of optimizing the chemical composition and technology of synthesis of the catalyst for the acetylene hydrocarbons hydrogenation in industrial streams of butadiene and ethyl-vinylacetylene fractions, the influence of the palladium initial compound nature, the active component concentration, the promotion by cobalt, the molar ratio of palladium to cobalt, the phase composition of the supporter on physical chemical properties, and the activity and selectivity to 1,3-butadiene of the catalysts was studied. The effect of acidic-base characteristics of the supporter on its ability to oligomerize unsaturated hydracarbons has been investigated. It has been established, than the δ-Al₂O₃ supporter is characterized by a low concentration of Bronsted and Lewis acidic sites, decreasing the quantity of oligomers formed on its surface. The optimal composition of the non-promoted KGV-07 catalyst, recommended for the raw butadiene fraction hydrogenation, is 0.5% of Pd deposited from palladium acetate on δ-Al₂O₃ with palladium particles of 16 nm in size, on which the vinylacetylene conversion of 100% and the selectivity to 1,3-butadiene of 69.9% are reached at a temperature of 20°C at the reactor input, hourly space velocity (HSV) of hydrocarbon raws of 700 h⁻¹, molar ratio of hydrogen to ethyl-vinylacetylenes of 4: 1, summary concentration of 49% of acetylene hydrocarbons, and 1.5% of 1,3-butadiene in hydrocarbon raws. The synthesis of the cobalt-promoted KGVP-07 catalyst with 0.5% of Pd deposited from palladium acetylacetonate on δ-Al₂O₃ and molar ratio of Pd: Co = 1: 1 has been developed for the hydrogenation of an ethyl-vinylacetylene fraction with a concentration of acetylene hydrocarbons to 6 wt %, with the vinylacetylene conversion of 100% and the selectivity to 1,3-butadiene of 61.3%, at HSV of the hydrocarbon stream of 700 h⁻¹, temperature of 6°C at the reactor input, and molar ratio of hydrogen to ethyl-vinylacetylene admixtures of 4: 1. Promotion by cobalt leads to the formation of palladium particles at the zero oxidation level and to an increase in their average size from 11 to 14 nm in comparison with the non-promoted Pd-catalyst. In the work, IR-spectroscopy, transmission electron microscopy (TEM), and physicochemical methods have been used to characterize the catalysts texture and supporter phase composition. Pilot tests of the KGV-07 and KGVP-07 catalysts on the Etilen plant unit have proven the correctness of the choice for the catalysts’ optimal chemical composition.     

Hydrocarbon conversions with some intermetallic catalysts

The intermetallic pseudo-binary alloys of the general type ZrRh_3-xPd_x and ZrRh_3-xRu_x (0 < × < 3) have been prepared by argon arc melting and melt quenching of the constituent elements. The alloys were powdered and employed as catalysts for (i) hydrogenation of oct-1-yne in the liquid phase at 101.32 kPa total pressure and 70°C, (ii) hydrogenation of buta-1,3-diene in the gas phase at 101.32 kPa total pressure in the temperature range 45–225°C, and (iii) hydrogenolysis of n-pentane in the gas phase at 101.32 kPa total pressure and in the temperature range 200–400°C. Activity and selectivity measurements were made with respect to (i) alkene formation for the hydrogenation reactions, and (ii) C₂ + C₃-alkane formation for the hydrogenolysis reaction. The activity of the alloy series appears to correlate to some degree with the electronic properties and hydrogen sorption capacity of the intermetallic alloys. Auger electron spectroscopy measurements revealed that for ZrRh_3-xPd_x alloys both the surface and bulk compositions were in good agreement; this behaviour is contrasted briefly with that of CeRh_3-xPd_x alloys which, unlike ZrRh_3-x alloys, suffered significant oxygen interaction in the surface and sub-surface layers, although this did not affect Rh:Pd ratios. Catalysts that were active for hydrogenation were inactive for hydrogenolysis and vice versa. However, selectivity values for the hydrogenation reactions generally reflected the behaviour of the predominant noble transition metal. Again, the behaviour of ZrRh_3-xPd_x and CeRh_3-x alloys is contrasted, since the latter were more selective for butene formation from buta-1,3-diene, and attributed to the oxygen Contamination of the surface. Further more, the selectivity of both ZrPd and CePd, for 1-octyne and butu-l j-dene hydrogenation was significantly greater than that of palladium by virtue of the fact that the intermetallics were found to be largely inactive for alkene hydrogenation.     

Enantioselective Hydrogenation of N‐Acetyldehydroamino Acids over Supported Palladium Catalysts

The enantioselective hydrogenation of two N‐acetyldehydroamino acids over Cinchona alkaloid‐modified, supported palladium catalysts has been studied. Moderate enantioselectivities, up to 36 %, were obtained in the hydrogenation of 2‐acetamidocinnamic acid over cinchonidine‐modified Pd/TiO₂ under low hydrogen pressure. Increase in the pressure or use of benzylamine as additive led to a gradual decrease in the enantiomeric excess and eventually inversion of the sense of the enantioselectivity. On the contrary, the optical purity of the product resulting from the hydrogenation of 2‐acetamidoacrylic acid was significantly increased by addition of benzylamine to the reaction mixture. Enantiomeric excess values up to 58 % and 60 % were obtained over Pd/Al₂O₃ modified by cinchonidine and cinchonine, respectively. These optical purities are the best obtained in the hydrogenation of dehydroamino acid derivatives over chirally modified heterogeneous metal catalysts.     

Effects of 1,2‐butadiene on the anionic copolymerization of styrene and 1,3‐butadiene in the presence of polar additives

1,2‐Butadiene is shown to be a chain terminating/transferring agent in butyllithium‐initiated diene polymerization. The influence of 1,2‐butadiene on the anionic copolymerization of 1,3‐butadiene and styrene is investigated using n‐butyllithium as initiator and tetrahydrofuran or N,N,N′,N′‐tetramethylethylenediamine as polar additive. A decrease of copolymerization rate is observed on the addition of 1,2‐butadiene. On introducing 1,2‐butadiene, the number average molecular weight (M_n ) decreases and the molecular weight distribution broadens. The vinyl content of copolymer increases slightly with an increase of 1,2‐butadiene. During the copolymerization, 1,2‐butadiene in the presence of a high ratio of polar additives to n‐butyllithium greatly decreases the copolymerization rate, resulting in a lower value of M_n and a narrower molecular weight distribution than that found for a low ratio of polar additives to n‐butyllithium. This evolution can be explained by the base‐catalyzed isomerization of 1,2‐butadiene to form 1‐butylene in the presence of polar additives. With an increasing amount of 1,2‐butadiene, the vulcanized rubber exhibits an increased rolling resistance and a reduced wet skid resistance owing to the decrease of coupling efficiency. These results further indicate the activity of alkynyllithium derivatives produced by the reaction of alkyllithium and 1‐butyne is less than that of the alkyllithium. Copyright © 2007 Society of Chemical Industry     

Carbon‐Carbon Double Bond versus Carbonyl Group Hydrogenation: Controlling the Intramolecular Selectivity with Polyaniline‐Supported Platinum Catalysts

The use of polyaniline (PANI) as catalyst support for heterogeneous catalysts and their application in chemical catalysis is hitherto rather poorly known. We report the successful synthesis of highly dispersed PANI‐supported platinum catalysts (particle sizes between 1.7 and 3.7 nm as revealed by transmission electron microscopy, TEM) choosing two different approaches, namely (i) deposition‐precipitation of H₂PtCl₆ onto polyaniline, suspended in basic medium (DP method) and, (ii) immobilization of a preformed nanoscale platinum colloid on polyaniline (sol‐method). The PANI‐supported platinum catalysts were applied in the selective hydrogenation of the α,β‐unsaturated aldehyde citral. In order to benchmark their catalytic performance, citral hydrogenation was also carried out by using platinum supported on the classical support materials silica (SiO₂), alumina (Al₂O₃), active carbon and graphite. The relations of the structural characteristics and surface state of the catalysts with respect to their hydrogenation properties have been probed by EXAFS and XPS. It is found that the DP method yields chemically prepared PtO₂ on polyaniline and, thus, produces a highly dispersed and immobilized Adams catalyst (in the β‐PtO₂ form) which is able to efficiently hydrogenate the conjugated CC bond of citral (selectivity to citronellal=87%), whereas reduction of the CO group occurs with polyaniline‐supported platinum (selectivity to geraniol/nerol=78%) prepared via the sol‐method. The complete reversal of the selectivity between the preferred hydrogenation of the conjugated CC or CO group is not only particularly useful for the selective hydrogenation of α,β‐unsaturated aldehydes but also unveils the great potential of conducting polymer‐supported precious metals in the field of hitherto barely investigated chemical catalysis.     

Polymer‐based catalysts for toluene hydrogenation

Crosslinked poly(4‐vinylpyridine‐co‐styrene) was synthesized by radical polymerization. Catalysts having 1 wt % Pd were obtained by impregnation of a copolymer, poly(4‐vinylpyridine‐co‐styrene) with a Pd colloidal dispersion. We modified metal particle sizes by changing the aging period of the colloidal dispersion, with the average size in the range of 2.5–4.3 nm. The most probable structure of the metal cluster attached to the polymers is described. X‐ray diffraction, transmission electron microscopy (TEM), and H₂? O₂ titrations were used as characterization techniques. The H₂ consumption during titration was extremely low, and the calculated metal dispersion was between 15 and 25 times lower than those estimated from TEM. This suggests that the Pd crystals were almost completely covered by the polymer. The vapor‐phase hydrogenation of toluene on resins supported Pd catalysts were studied. The catalysts in the hydrogenation of toluene exhibited low activity, and the obtention of significant selectivities to partial hydrogenation products (close to 60 mol %) was remarkable. The results are explained in terms of a significant decrease in the hydrogenation capacity due to the coverage of metal particles by the resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 381–385, 2002     

Toward economical purification of styrene monomers: Eggshell Mo2C for front‐end hydrogenation of phenylacetylene

An eggshell Mo₂C catalyst which is designed from the rapid combination of molybdate with melamine is described. In contrast to Pd‐based catalysts, the eggshell Mo₂C operates effectively with a wide‐concentration window in high‐temperature gas phase hydrogenation of phenylacetylene, thus, an economical and energy‐efficient front‐end purification of styrene monomers might be possible. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2522–2531, 2015     

Donor‐Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium‐Catalyzed Alkynylation and Platinum‐Catalyzed Hydrogenation in Ionic Liquids

The straightforward synthesis of a new donor‐stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3‐dimethylimidazolium‐2‐carboxylate 1 is described. The obtained ligand exhibits a very strong π‐acceptor character, comparable to that of triphenyl phosphite [P(OPh)₃] or of tris‐halogenophosphines, with a ν_CO(A₁) at 2087 cm⁻¹ for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium‐catalyzed aryl alkynylation and in the platinum‐catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In C C bond cross‐coupling we observed that the increase of the π‐acceptor character in ligand 3d , due to the introduction of an additional electron‐withdrawing group, provides a very efficient catalyst in the alkynylation reaction of aryl bromides with phenylacetylene, including the deactivated 4‐bromoanisole or the sterically hindered 2‐bromonaphthalene. The catalytic activity decreases with recycling due to the sensitiveness of ligands to protonation in the ionic phase. Conversely, a multiple recycling of the metal/ligand system in non‐acidic media was achieved from platinum‐catalyzed hydrogenation of m‐chloronitrobenzene. The catalytic results obtained by employing the complex of platinum(II) chloride with 3a [trans‐PtCl₂( 3a )₂] in comparison with the non‐ionic related trans‐tris(triphenylphosphine)platinum dichloride [trans‐PtCl₂(PPh₃)₂] complex clearly indicate that the simultaneous existence of a strong π‐acceptor character and a positive charge within the ligand 3a significantly increases the life‐time of the platinum catalyst. The selectivity of the reaction is also improved by decreasing the undesirable formation of dehalogenation products. This cationic platinum complex trans‐PtCl₂( 3a )₂ is the first example of a highly selective catalyst for hydrogenation of chloronitroarenes immobilized in an ionic liquid phase. The system was recycled six times without noticeable metal leaching in the organic phase, and no loss of activity.     

Influence of imine‐carbon substituent in 6‐bromo‐2‐iminopyridine‐based cobalt(II) complexes on 1,3‐butadiene polymerization

6‐Bromo‐2‐iminopyridine cobalt(II) complexes bearing different imine‐carbon substituents ( Co1 – Co7 ) were synthesized and subsequently employed for 1,3‐butadiene polymerization. All the complexes were identified using Fourier transform infrared spectra and elemental analysis, and complexes Co1 and Co3 were further characterized using single‐crystal X‐ray diffraction analysis, demonstrating they adopted distorted trigonal bipyramidal and tetrahedral geometries, respectively. Activated by methylaluminoxane, these complexes exhibited high cis‐1,4 selectivity, and the activity was highly dependent on the substituent at the imine‐carbon position of the ligand. Addition of PPh₃ to the polymerization systems could enhance the catalytic activity and simultaneously switched the selectivity from cis‐1,4 to cis‐1,2 manner. On the basis of the obtained results, a plausible mechanism involving the regulation of selectivity and activity is proposed. © 2019 Society of Chemical Industry     

Study on liquid‐phase hydrogenation of paranitrotoluene over Ru‐based catalysts

This paper presented a study on the role of yttrium addition to Ru‐based catalysts for liquid phase paranitrotoluene hydrogenation reaction. An impregnation‐precipitation method was used for preparation of a series of yttrium doped Ru/NaY catalysts with yttrium content in the range of 0.0026–0.0052 g/g. Properties of the obtained samples were characterized and analyzed by X‐ray diffraction (XRD), H₂‐TPR, Transmission electron microscopy (TEM), ICP atomic emission spectroscopy, and Nitrogen adsorption‐desorption. The results revealed that catalytic activity of NaY supported Ru catalysts increased with the yttrium content at first, then decreased with the further increase of yttrium content. When yttrium content was 0.0033 g/g, a Ru‐Y/NaY² catalyst showed the most excellent performance of paranitrotoluene hydrogenation reaction (paranitrotoluene conversion and the selectivity toward P‐methyl‐cyclohexylamine reached 99.9 % and 82.5 %, respectively). In addition, to compare with the performance of Ru‐Y/NaY catalysts, the active carbon supported Ru catalysts were prepared using the same method in view of its higher surface area and adsorption capacity. Finally, the effect of solvent on the reaction over Ru‐Y/NaY² catalyst has been investigated, it was found that the best performance of paranitrotoluene hydrogenation reaction took place in protic solvents (isopropanol and ethanol). This was mainly ascribed to their polarity and hydrogen‐bond accepting capability.