Catalysts For Hydrogenation Of Alkenes Research Articles

The structural and electronic promoting effect of nitrogen-doped carbon nanotubes on supported Pd nanoparticles for selective olefin hydrogenation

A high-performance Pd catalyst for selective olefin hydrogenation was synthesized by supporting Pd nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). X-ray diffraction, hydrogen chemisorption, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize Pd supported on NCNTs and nitrogen-free oxygen-functionalized CNTs (OCNTs). The Pd nanoparticles were stabilized on NCNTs with narrower size distribution compared with OCNTs. The XPS analysis revealed that the nitrogen functional groups favor the reduction of Pd on CNTs suggesting an electronic promoter effect. The Pd/NCNT catalyst showed extraordinary catalytic performance in terms of activity, selectivity and stability in the selective hydrogenation of cyclooctadiene, which is related to the structural and electronic promoting effect of the NCNT support.

A stable 16-electron iridium(iii) hydride complex grafted on SBA-15: a single-site catalyst for alkene hydrogenation

The dihydride pincer complex [IrH2(POCOP)] reacts with surface silanols of mesoporous silica (SBA-15) to give the coordinatively unsaturated, yet stable hydridesiloxo Ir(III) species [IrH(O-SBA-15)(POCOP)]. The silica-grafted complex catalyses the hydrogenation of ethene and propene at low temperature and pressure without prior activation.

Pd nanoparticles immobilized on boehmite by using tannic acid as structure-directing agent and stabilizer: a high performance catalyst for hydrogenation of olefins

Boehmite-supported Pd nanoparticles (Pd–TA–boehmite) were successfully synthesized by a hydrothermal method using tannic acid as the structure-directing agent as well as stabilizer. The physicochemical properties of the Pd–TA–boehmite catalyst were well characterized by XPS, XRD, N2 adsorption/desorption, and TEM analyses. Catalytic hydrogenation of olefins was used as the probe reaction to evaluate the activity of the Pd–TA–boehmite catalyst. For comparison, the Pd–boehmite catalyst prepared without tannic acid was also employed for olefin hydrogenation. For all the investigated substrates, the Pd–TA–boehmite catalyst exhibited superior catalytic performance than the Pd–boehmite catalyst. For the example of hydrogenation of allyl alcohol, the initial hydrogenation rate and selectivity of the Pd–TA–boehmite catalyst were 23,520 mol/mol h and 99 %, respectively, while those of the Pd–boehmite catalyst were only 14,186 mol/mol h and 93 %, respectively. Additionally, the hydrogenation rate of the Pd–TA–boehmite catalyst could still reach 20,791 mol/mol h at the 7th cycle, which was much higher than that of the Pd–boehmite catalyst (5,250 mol/mol h) at the 4th cycle, thus showing an improved reusability.

Alkene Hydrogenation Catalyzed by Nickel Hydride Complexes of an Aliphatic PNP Pincer Ligand

AbstractTo investigate metal–ligand cooperativity as a strategy for promoting nickel‐catalyzed alkene hydrogenation, cationic and neutral nickel(II) hydride complexes of the aliphatic pincer ligand PNHPCy {PNHPCy = HN[CH2CH2P(Cy)2]2} have been synthesized and characterized. Cationic hydride complex [(PNHPCy)Ni(H)]BPh4 (2) catalyzed the hydrogenation of styrene and 1‐octene under mild conditions. Only low conversion was observed in the hydrogenation of 3,5‐dimethoxybenzaldehyde using 2. The neutral hydride complex (PNPCy)Ni(H) (3) was also found to be an alkene hydrogenation catalyst. Mechanistic experiments suggest that for catalyst 2, the hydrogenation reaction proceeds through a pathway involving initial insertion of the alkene into the Ni–H bond. Contrary to the initial hypothesis, reactivity comparisons with the methyl‐substituted hydride complex [(PNMePCy)Ni(H)]BPh4 {PNMePCy = (CH3)N[CH2CH2P(Cy)2]2} suggest that metal–ligand cooperativity is not involved in these rare examples of mild and homogeneous nickel hydrogenation catalysis.

ChemInform Abstract: Iron—Iron Oxide Core—Shell Nanoparticles Are Active and Magnetically Recyclable Olefin and Alkyne Hydrogenation Catalysts in Protic and Aqueous Media.

AbstractThe catalyst shows selectivity towards the less activated double bonds and tolerates the presence of air and water.

ChemInform Abstract: Shape and Size Controlled Pt Nanocrystals as Novel Model Catalysts

AbstractReview: 58 refs.

Enantiopure C1-Symmetric Bis(imino)pyridine Cobalt Complexes for Asymmetric Alkene Hydrogenation

Enantiopure C(1)-symmetric bis(imino)pyridine cobalt chloride, methyl, hydride, and cyclometalated complexes have been synthesized and characterized. These complexes are active as catalysts for the enantioselective hydrogenation of geminal-disubstituted olefins.

Iron-iron oxide core–shell nanoparticles are active and magnetically recyclable olefin and alkyne hydrogenation catalysts in protic and aqueous media

We report for the first time the use of iron-iron oxide core-shell nanoparticles for the hydrogenation of olefins and alkynes under mild conditions in ethanol and in an aqueous medium. This catalyst proves robust towards the presence of oxidants, such as oxygen and water, is magnetically recoverable and shows selectivity towards the less activated double bonds.

Shape and Size Controlled Pt Nanocrystals as Novel Model Catalysts

A tremendous development of nanotechnology enabled us to prepare precisely structure-controlled nanocrystals (NCs). Recently, such structure controlled NCs have been applied as model catalysts with controlled active sites to evaluate reaction mechanisms. Here, we review our recent works on preparation of shape controlled Pt NCs, such as cube and wire, and on application as model catalysts for olefin hydrogenation to assess active Pt sites. A hydrogen reduction method of Pt(II) ion was adopted in an aqueous phase to prepare Pt cube in the presence of shape forming agent (NaI) and organic protective agent (sodium polyacrylate or sodium succinate). We succeed to prepare Pt cube with high size and shape selectivity, followed by very small Pt cube of less than 3 nm. Such simultaneous control of both size and shape of Pt NCs has been successfully achieved by the sophisticated tuning of multiple conditions for the growth kinetics of Pt nuclei during hydrogen reduction of PtCl4 2− in aq. N-, N-dimethylformamide (DMF) solution. The key strategy is to produce small Pt nuclei and to avoid the excessive growth of Pt nuclei, in conjunction with face selective adsorption of anionic protective and shape-forming agents by the control of solvent system. For the preparation of Pt nanowires with high anisotropy, template-assisted methods have been usually used. We have developed facile liquid phase preparation method at room temperature in air without any template. The key factors of the method are: firstly, to use aqueous organic solvent system to control solvent polarity; secondly, to use co-solvent DMF as shape forming agent; thirdly, to use excess NaBH4 as a stabilizer of Pt nuclei to prevent formation of conventional particles. Single-crystalline Pt nanowires of 2 nm diameter and more than micron length were easily obtained by the reduction of Pt(IV) with excess NaBH4 in water–DMF–toluene solution (1:8:5 volume ratio) in a short reaction period of 3 h. Then, we have applied shape-controlled Pt NCs protected with PAA prepared by our original methods, such as cube, tetrahedron and wire, as model catalysts for olefin (cis- and trans-stilbenes) hydrogenation in ethanol to evaluate the active facet of Pt catalysts; e.g., Pt(111) or Pt(100). The estimated TOF values for the hydrogenation of cis- and trans-stilbene decreased in the order: cube > cuboctahedron > tetrahedron ~ nanowire. This tendency indicates that Pt(100) show high activity compared with Pt(111). The result is compatible with measurement of XPS and Raman spectra, suggesting strong adsorption of reactant on Pt(100). Hydrogenation of olefins (1-hexene and cyclohexene) has been carried out over Pt cubes with different sizes (8.2–10.1 nm) as catalysts to get information about active sites of Pt catalysts, e.g., flat facet or edge/corner atoms. The results of similar TOF values among Pt cubes with different sizes imply that the active sites are flat facets.

Axially chiral dimeric Ir and Rh complexes bridged by flexible NHC ligands

A family of Ag complexes of the type [{BnN(CH2CH2RIm)2}Ag]·[AgX2] (X=I, RIm=1-methylimidazole (3a); X=Cl, RIm=1-tert-butylimidazole (3b), 1-benzylimidazole (3c) or 1-methylbenzimidazole (3d)) or [{BnN(CH2CH2CH2RIm)2}Ag]·[AgCl2] (RIm=1-methylimidazole (4a), 1-tert-butylimidazole (4b), 1-benzylimidazole (4c) or 1-methylbenzimidazole (4d)) with a flexible unsaturated linker connecting the two NHC ligands has been prepared. These silver complexes undergo facile transmetalliation with [Ir(COD)Cl]2 to generate the bimetallic species (COD)ClIr{BnN(CH2CH2RIm)2}IrCl(COD) (RIm=1-methylimidazole (5a), 1-tert-butylimidazole (5b), 1-benzylimidazole (5c) or 1-methylbenzimidazole (5d)) or (COD)ClIr{BnN(CH2CH2CH2RIm)2}IrCl(COD) (RIm=1-methylimidazole (6a), 1-tert-butylimidazole (6b), 1-benzylimidazole (6c) or 1-methylbenzimidazole (6d)) with a bridging bidentate NHC ligand. A similar reaction can be performed using [Rh(COD)Cl]2 to generate the analogous Rh species (COD)ClRh{BnN(CH2CH2CH2RIm)2}RhCl(COD) (RIm=1-methylimidazole (7a), 1-benzylimidazole (7c) or 1-methylbenzimidazole (7d)). Complexes 5d, 6d and 7d were characterized by X-ray crystallography. All of our new Rh and Ir species possess axial chirality and are prepared as a mixture of isomers. However, crystals of 5d, 6d and 7d contain only one diastereomer. Dissolution of the diastereometrically pure crystals results in epimerization and the formation of an equilibrium mixture. Our new Ir complexes are active catalysts for both olefin and transfer hydrogenation and we present a comparison of their catalytic activity based on the linker length of the ligand.

Silica–Dendrimer Core–Shell Microspheres with Encapsulated Ultrasmall Palladium Nanoparticles: Efficient and Easily Recyclable Heterogeneous Nanocatalysts

We report the synthesis, characterization, and catalytic properties of novel monodisperse SiO(2)@Pd-PAMAM core-shell microspheres containing SiO(2) microsphere cores and PAMAM dendrimer-encapsulated Pd nanoparticle (Pd-PAMAM) shells. First, SiO(2) microspheres, which were prepared by the Stöber method, were functionalized with vinyl groups by grafting their surfaces with vinyltriethoxysilane (VTS). The vinyl groups were then converted into epoxides by using m-chloroperoxybenzoic acid. Upon treatment with amine-terminated G4 poly(amidoamine) (PAMAM) dendrimers, the SiO(2)-supported epoxides underwent ring-opening and gave SiO(2)@PAMAM core-shell microspheres. Pd nanoparticles within the cores of the SiO(2)-supported PAMAM dendrimers were synthesized by letting Pd(II) ions complex with the amine groups in the cores of the dendrimers and then reducing them into Pd(0) with NaBH(4). This produced the SiO(2)@Pd-PAMAM core-shell microspheres. The presence of the different functional groups on the materials was monitored by following the changes in FTIR spectra, elemental analyses, and weight losses on thermogravimetric traces. Transmission electron microscopy (TEM) images showed the presence of Pd nanoparticles with average size of 1.56 ± 0.67 nm on the surface of the monodisperse SiO(2)@Pd-PAMAM core-shell microspheres. The SiO(2)@Pd-PAMAM core-shell microspheres were successfully used as an easily recyclable catalyst for hydrogenation of various olefins, alkynes, keto, and nitro groups, giving ~100% conversion and high turnover numbers (TONs) under 10 bar H(2) pressure, at room temperature and in times ranging from 10 min to 3 h. In addition, the SiO(2)@Pd-PAMAM core-shell microspheres were proven to be recyclable catalysts up to five times with barely any leaching of palladium into the reaction mixture.

Proline‐Based P,O Ligand/Iridium Complexes as Highly Selective Catalysts: Asymmetric Hydrogenation of Trisubstituted Alkenes

P,O joins the mix: P,O ligands (L1) form efficient iridium catalysts for the asymmetric hydrogenation of olefins. The proline-derived ligands lead to high enantioselectivities with several classes of alkenes, most notably with α,β-unsaturated carboxylic esters and ketones, where they match or even surpass the ee values reported for the best N,P and C,N ligands. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

ChemInform Abstract: Zwitterionic Iridium Complexes with P,N‐Ligands as Catalysts for the Asymmetric Hydrogenation of Alkenes.

AbstractA variety of imidazoline‐, or oxazoline‐based chiral iridium—P,N ligand complexes, e.g. IPOXA, IPOXB, is prepared and studied as catalyst in the hydrogenation of various olefins.

Zwitterionic Iridium Complexes with P,N‐Ligands as Catalysts for the Asymmetric Hydrogenation of Alkenes

Several zwitterionic iridium complexes based on chiral P,N-ligands with imidazoline or oxazoline donors and anionic tetraarylborate or aryltrifluoroborate substituents have been synthesized. The corresponding cationic analogues have also been prepared, to evaluate the effect of the covalent linkage between the anion and the cationic metal complex in catalytic reactions. The respective pairs of structurally analogous precatalysts have been compared for their efficacies in the asymmetric hydrogenation of unfunctionalized olefins. In most cases, the anionic derivatization has virtually no influence on the asymmetric induction of the iridium complex. This is in accordance with X-ray structural studies, which have shown that the chiral environment of the cationic metal center is not affected by the anionic substituent. Depending on the nature of the counterion employed, the zwitterionic catalysts proved to be significantly more reactive than their cationic counterparts in nonpolar solvents.

Recyclable mesoporous silica-supported chiral ruthenium-(NHC)NN-pincer catalysts for asymmetric reactions

New stable chiral [RuHClCO((NHC)NN)] and [RuCl2(p-cymene)((NHC)NN)] pincer complexes with a pendant silyloxy group ((NHC)NN: (S)-1-((6-((3-aryl-2,3-dihydro-1H-imidazol-1-yl)methyl)pyridin-2-yl)methyl); R-N-(3-(triethoxysilyl)propyl)pyrrolidine-2-carboxamide, aryl = mesityl, 2,6-diisopropylphenyl; R = Me, Ph) were synthesized and grafted onto a mesoporous silica MCM-41 through the siloxane linkage, and the resulting supported ruthenium catalysts were highly active and recyclable catalysts for the asymmetric hydrogenation of alkenes and cyclopropanation of styrenes. The solid catalysts were characterized with a variety of methods including solid state cross-polarization magic-angle spinning (CP MAS) 13C NMR, FT-IR, and elemental analysis. Excellent activity and enantioselectivity was observed for these supported Ru-catalysts owing to readily accessible and uniform catalytic sites within the large channels of MCM-41 and short diffusion lengths for the organic compounds. The high accessibility introduced by the structure of the support allows the preparation of highly efficient immobilized catalysts which can duplicate the activity of the homogeneous analogues. No deactivation of the catalysts was observed after repeated recycling.

Iridium‐Catalyzed Asymmetric Hydrogenation of Unfunctionalized, Trialkyl‐Substituted Olefins

Chiral iridium complexes with bicyclic pyridine-based N,P ligands have emerged as efficient catalysts for the enantioselective hydrogenation of unfunctionalized trialkyl-substituted olefins. Optimization of the reaction conditions by variation of the solvent, pressure, and temperature led to enantiomeric excesses of up to 99%. Three pure alkenes, (E)-2-cyclohexyl-2-butene and (E)- and (Z)-3,4-dimethyl-2-pentene were converted into the corresponding chiral alkanes with 97%, 94%, and 93% ee, respectively. Hydrogenation of the three C=C bonds of both α- and γ-tocotrienyl acetate led to α- and γ-tocopheryl acetate with very high diastereoselectivity. The same catalysts were successfully applied in the hydrogenation of trisubstituted alkenes with a carboxylic ester or a keto group in the γ position. This reaction was used as a key step in a highly enantioselective synthesis of the pheromone of the caddisfly Hesperophylax occidentalis. The hydrogenation of a structurally analogous allylic alcohol also gave high enantioselectivities.

Synthesis of Oxygen- and Sulfur-Bridged Dirhodium Complexes and Their Use As Catalysts in the Chemoselective Hydrogenation of Alkenes

Oxygen-bridged and sulfur-bridged rhodium homobimetallic complexes were synthesized as air-stable crystals by using 2,6-bis(phosphanylmethyl)phenolate and -thiophenolate as the ligands, respectively. The oxygen-bridged dirhodium complex has a symmetrical structure where the carbon atom at the ipso position, oxygen, and two rhodium atoms are located in the same plane. It is thermally stable compared to the sulfur-bridged dirhodium complex and shows catalytic activity for hydrogenation of alkenes with high chemoselectivity.

Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure on their activity as catalysts for olefin hydrogenation

Recent developments in nanotechnology have led to the production of new materials with a wide array of applications, particularly in catalysis. Because of their small size, nanoparticles have a maximized surface-to-volume ratio, thus making them attractive targets for use as catalytic structures; however, the number of analytical techniques available to fully characterize materials on such a size scale is quite limited. As a result, a complete understanding of the entire nanoparticle structure remains unclear, especially when considering the active structural motif from which the specific activity arises. Metallic Pd materials have been widely studied due to their immense potential as catalysts for reactions such as olefin hydrogenation and C-C bond synthesis. These materials require surface passivants to act as ligands and stabilize the nanoparticles against aggregation and bulk formation. These ligands have the added value to function as gates that selectively allow reagents to reach the active surface of the Pd nanoparticles for chemical turnover. This accounts for the observed selectivities of the catalysts with the corresponding changes in the turnover frequency values. Here we present a broad overview of recent advances in the use of Pd nanoparticles for the industrially important hydrogenation reaction with a focus on characterizing and understanding the base structural effects that give rise to the catalytic activity.

Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins

Five-coordinated rhenium(I) hydride complexes of the type [Re(Br)(H)(NO)(PR3)2] (R = Cy 2a, iPr 2b) were prepared from [Re(Br)2(NO)(PR3)2(η2-H2)] (R = Cy 1a, iPr 1b) via deprotonation of the η2-H2 ligands with various bases. Filling the vacant site of 2a or 2b by various less bulky two-electron donors produced the 18-electron complexes [Re(Br)(H)(NO)(PR3)2(L)] (L = O2 3, CH2═CH2 4, acetylene 5, H2 6, CO 7, CH3CN 8). The influence of the trans-coordinated ligand on the Re−H bond was examined. The 1H NMR chemical shift of the hydride depends on L in the order O2 > acetylene > CH2═CH2 > H2 > CO > CH3CN. The reactions of 2a or 2b with the IMes or SIMes ligands afforded the five-coordinated complex [Re(Br)(H)(NO)(PR3)(NHC)] (NHC = IMes 9 (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), SIMes 10 (SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)) via replacement of one phosphine. The reaction of 2a or 2b with n-BuLi leads to the formation of the n-butene-coordinated dihydride compl...

“Click” Polymer‐Supported Palladium Nanoparticles as Highly Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling Reactions under Ambient Conditions

AbstractComplexation of palladium(II) acetate [Pd(OAc)2] or dipotassium tetrachloropalladate [K2PdCl4] to “click” polymers functionalized with phenyl, ferrocenyl and sodium sulfonate groups gave polymeric palladium(II)‐triazolyl complexes that were reduced to “click” polymer‐stabilized palladium nanoparticles (PdNPs). Transmission electron microscopy (TEM) showed that reduction using sodium borohydride (NaBH4) produced PdNPs in the 1–3 nm range of diameters depending on the nature of the functional group, whereas slow reduction using methanol yielded PdNPs in the 22–25 nm range. The most active of these PdNPs (0.01% mol Pd), stabilized by poly(ferrocenyltriazolylmethyl)styrene, catalyzed the hydrogenation of styrene at 25 °C and 1 atm hydrogen, with turnover numbers (TONs) of 200,000. When stabilized by the water‐soluble poly(sodium sulfonate‐triazolylmethyl)styrene, the PdNPs (0.01% mol Pd) catalyze the Suzuki–Miyaura coupling between iodobenzene (PhI) and phenylboronic acid [PhB(OH)2] in water/ethanol (H2O/EtOH) at 25 °C with TONs of 8,200. This high catalytic activity is comparable to that obtained with “click” dendrimer‐stabilized PdNPs under ambient conditions.