624-29-3Relevant academic research and scientific papers
Discovery of a Neutral 40-PdII-Oxo Molecular Disk, [Pd40O24(OH)16{(CH3)2AsO2}16]: Synthesis, Structural Characterization, and Catalytic Studies
Bhattacharya, Saurav,Bons, Anton-Jan,Cadot, Emmanuel,Espenship, Michael Forrester,Haouas, Mohamed,Jaensch, Helge,Kortz, Ulrich,Laskin, Julia,Ma, Xiang,Mougharbel, Ali S.,Stuerzer, Tobias,Su, Pei,Taffa, Dereje H.,Wark, Michael
, p. 17339 - 17347 (2021/11/17)
We report on the synthesis and structural characterization of a giant, discrete, and neutral molecular disk, [Pd40O24(OH)16{(CH3)2AsO2}16] (Pd40), comprising a 40-palladium-oxo core that is capped by 16 dimethylarsinate moieties, resulting in a palladium-oxo cluster (POC) with a diameter of μ2 nm. Pd40, which is the largest known neutral Pd-based oxo cluster, can be isolated either as a discrete species or constituting a 3D H-bonded organic-inorganic framework (HOIF) with a 12-tungstate Keggin ion, [SiW12O40]4- or [GeW12O40]4-. 1H and 13C NMR as well as 1H-DOSY NMR studies indicate that Pd40 is stable in aqueous solution, which is also confirmed by ESI-MS studies. Pd40 was also immobilized on a mesoporous support (SBA15) followed by the generation of size-controlled Pd nanoparticles (diameter μ2-6 nm, as based on HR-TEM), leading to an effective heterogeneous hydrogenation catalyst for the transformation of various arenes to saturated carbocycles.
Polysilane-Immobilized Rh-Pt Bimetallic Nanoparticles as Powerful Arene Hydrogenation Catalysts: Synthesis, Reactions under Batch and Flow Conditions and Reaction Mechanism
Miyamura, Hiroyuki,Suzuki, Aya,Yasukawa, Tomohiro,Kobayashi, Shu
supporting information, p. 11325 - 11334 (2018/09/06)
Hydrogenation of arenes is an important reaction not only for hydrogen storage and transport but also for the synthesis of functional molecules such as pharmaceuticals and biologically active compounds. Here, we describe the development of heterogeneous Rh-Pt bimetallic nanoparticle catalysts for the hydrogenation of arenes with inexpensive polysilane as support. The catalysts could be used in both batch and continuous-flow systems with high performance under mild conditions and showed wide substrate generality. In the continuous-flow system, the product could be obtained by simply passing the substrate and 1 atm H2 through a column packed with the catalyst. Remarkably, much higher catalytic performance was observed in the flow system than in the batch system, and extremely strong durability under continuous-flow conditions was demonstrated (>50 days continuous run; turnover number >3.4 × 105). Furthermore, details of the reaction mechanisms and the origin of different kinetics in batch and flow were studied, and the obtained knowledge was applied to develop completely selective arene hydrogenation of compounds containing two aromatic rings toward the synthesis of an active pharmaceutical ingredient.
A new approach for the preparation of well-defined Rh and Pt nanoparticles stabilized by phosphine-functionalized silica for selective hydrogenation reactions
Llop Castelbou,Szeto,Barakat,Merle,Godard,Taoufik,Claver
supporting information, p. 3261 - 3264 (2017/03/20)
In this work, a new methodology for the synthesis of well-defined metallic nanoparticles supported on silica is described. This methodology is based on the surface control provided by SOMC. The nanoparticles are formed via the organometallic approach and are catalytically active in the hydrogenation of p-xylene, 3-hexyne, 4-phenyl-2 butanone, benzaldehyde, and furfural.
METHODS FOR SELECTIVELY HYDROGENATING SUBSTITUTED ARENES WITH SUPPORTED ORGANOMETALLIC CATALYSTS
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Paragraph 0036, (2016/06/28)
Methods for selectively hydrogenating substituted arenes with a supported organometallic hydrogenating catalyst are provided. An exemplary method includes contacting a substituted arene-containing reaction stream with hydrogen in the presence of a supported organometallic hydrogenating catalyst under reaction conditions effective to selectively hydrogenate the substituted arenes to the cis isomer with high selectivity. In this method, the supported organometallic hydrogenating catalyst includes a catalytically active organometallic species and a Br?nsted acidic sulfated metal oxide support.
Nanoheterogeneous ruthenium-containing catalysts based on dendrimers in the hydrogenation of aromatic compounds under two-phase conditions
Karakhanov,Maximov,Zolotukhina,Terenina,Vutolkina
, p. 491 - 502 (2016/07/29)
Nanoheterogeneous catalysts based on ruthenium nanoparticles dispersed in crosslinked dendrimer matrixes with a size of polymer particles of 100–500 nm show high activity in the hydrogenation of aromatic compounds under two-phase conditions. The addition of water to the reaction medium exerts a strong promoting effect on the activity of the catalysts: The turnover frequency increases by a factor of 3–90 depending on the substrate. When bimetallic (PdRu) nanoparticles are incorporated into the catalyst composition, the rate of benzene hydrogenation increases while the rate of transformation of substituted benzenes decreases.
Single-Face/All-cis Arene Hydrogenation by a Supported Single-Site d0 Organozirconium Catalyst
Stalzer, Madelyn Marie,Nicholas, Christopher P.,Bhattacharyya, Alak,Motta, Alessandro,Delferro, Massimiliano,Marks, Tobin J.
, p. 5263 - 5267 (2016/04/26)
The single-site supported organozirconium catalyst Cp?ZrBz2/ZrS (Cp?=Me5C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange. Stereocontrol is on: A single-site supported organozirconium catalyst exhibits unprecedented all-cis stereo/face-selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value-added fine chemicals.
Hydrogenation of arenes, nitroarenes, and alkenes catalyzed by rhodium nanoparticles supported on natural nanozeolite clinoptilolite
Baghbanian, Seyed Meysam,Farhang, Maryam,Vahdat, Seyed Mohammad,Tajbakhsh, Mahmood
, p. 128 - 136 (2015/07/15)
Abstract Nanozeolite clinoptilolite supported rhodium nanoparticles (Rh/NZ-CP) has been prepared and characterized by a variety of techniques, including XRD, BET, TEM, EDX, ICP-OES and XPS analysis. This nanomaterial contains 2 wt% Rh in the range of 5-20 nm metallic nanoparticles distributed on nanozeolite. The catalytic performance of Rh/NZ-CP was evaluated by the hydrogenation of arenes, nitroarenes, and alkenes under moderate reaction conditions. The prepared nanocatalyst can be facilely recovered and reused many times without significant decrease in activity and selectivity. The high catalytic activity, thermal stability and reusability, simple recovery and eco-friendly nature make present catalyst as a unique catalytic system, which is particularly attractive in green chemistry.
A mild route to solid-supported rhodium nanoparticle catalysts and their application to the selective hydrogenation reaction of substituted arenes
Moreno-Marrodan, Carmen,Liguori, Francesca,Mercadé, Elisabet,Godard, Cyril,Claver, Carmen,Barbaro, Pierluigi
, p. 3762 - 3772 (2015/07/01)
A clean route is described for the preparation of 1.3% (w/w) supported rhodium nanoparticle (3.0 ± 0.7 nm) catalysts onto commercial ion-exchange resins. Their application to the liquid-phase hydrogenation reaction of C=C bonds shows the most active species are obtained under catalytic conditions at room temperature and 1 bar H2. The heterogeneous catalyst shows excellent activity, selectivity and reusability in the hydrogenation reaction of alkenes and substituted arenes under very undemanding conditions. The results are discussed in terms of support effect on the catalytic efficiency.
Ligand effect in the Rh-NP catalysed partial hydrogenation of substituted arenes
Castelbou, Jessica Llop,Gual, Aitor,Mercade, Elisabet,Claver, Carmen,Godard, Cyril
, p. 2828 - 2833 (2013/09/24)
The Rh nanoparticles Rh1-Rh4 stabilised by the mono- and bidentate phosphine and phosphite ligands I-IV were synthesised, characterised and applied as catalysts in the partial hydrogenation of substituted arenes. In the case of disubstituted arenes, selectivities for the corresponding cyclohexene derivatives of up to 39% were achieved at ca. 40% conversion. The effect of parameters such as temperature and pressure was also examined. In the hydrogenation of styrene, very high selectivities for ethylbenzene were achieved with TOF values up to ca. 23500 h-1. All these results show that the catalytic performance of small Rh-NPs can be modulated by the appropriate choice of stabilising agents.
Moving from surfactant-stabilized aqueous rhodium (0) colloidal suspension to heterogeneous magnetite-supported rhodium nanocatalysts: Synthesis, characterization and catalytic performance in hydrogenation reactions
Pélisson, Carl-Hugo,Vono, Lucas L.R.,Hubert, Claudie,Denicourt-Nowicki, Audrey,Rossi, Liane M.,Roucoux, Alain
experimental part, p. 124 - 129 (2012/06/18)
Wet impregnation of pre-synthesized surfactant-stabilized aqueous rhodium (0) colloidal suspension on silica was employed in order to prepare supported Rh0 nanoparticles of well-defined composition, morphology and size. A magnetic core-shell support of silica (Fe3O4@SiO 2) was used to increase the handling properties of the obtained nanoheterogeneous catalyst. The nanocomposite catalyst Fe3O 4@SiO2-Rh0 NPs was highly active in the solventless hydrogenation of model olefins and aromatic substrates under mild conditions with turnover frequencies up to 143,000 h-1. The catalyst was characterized by various transmission electron microscopy techniques showing well-dispersed rhodium nanoparticles (～3 nm) mainly located at the periphery of the silica coating. The heterogeneous magnetite-supported nanocatalyst was investigated in the hydrogenation of cyclohexene and compared to the previous surfactant-stabilized aqueous Rh0 colloidal suspension and various silica-supported Rh0 nanoparticles. Finally, the composite catalyst could be reused in several runs after magnetic separation.
