589-16-2Relevant academic research and scientific papers
MOF-Mediated Synthesis of Supported Fe-Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis**
Darawsheh, Mohanad D.,Mazarío, Jaime,Lopes, Christian W.,Giménez-Marqués, Mónica,Domine, Marcelo E.,Meira, Debora M.,Martínez, Jordan,Mínguez Espallargas, Guillermo,O?a-Burgos, Pascual
, p. 13659 - 13667 (2020)
Metal–organic framework (MOF)-driven synthesis is considered as a promising alternative for the development of new catalytic materials with well-designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe-doped Pd nanoparticles that, in turn, are supported on iron oxide-doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.
Selective hydrodeoxygenation of acetophenone derivatives using a Fe25Ru75@SILP catalyst: a practical approach to the synthesis of alkyl phenols and anilines
Bordet, Alexis,Goclik, Lisa,Leitner, Walter,Walschus, Henrik
supporting information, p. 2937 - 2945 (2022/04/07)
A versatile synthetic pathway for the production of valuable alkyl phenols and anilines has been developed based on the selective hydrodeoxygenation of a wide range of hydroxy-, amino-, and nitro-acetophenone derivatives as readily available substrates. Bimetallic iron ruthenium nanoparticles immobilized on an imidazolium-based supported ionic liquid phase (Fe25Ru75@SILP) act as highly active and selective catalysts for the deoxygenation of the side-chain without hydrogenation of the aromatic ring. The catalytic system allows operation under continuous flow conditions with high robustness and flexibility as demonstrated for the alternating conversion of 3′,5′-dimethoxy-4′-hydroxyacetophenone and 4′-hydroxynonanophenone as model substrates.
Rh-PVP Catalyzed Reductive Amination of Phenols by Ammonia or Amines to Cyclohexylamines under Solvent-free Conditions
Chaudhari, Chandan,Nagaoka, Katsutoshi,Nishida, Yoshihide,Rumi, Saeki,Sato, Katsutoshi,Shiraishi, Masaya
supporting information, p. 81 - 84 (2022/01/12)
Colloidal metal nanoparticles were examined for reductive amination of phenol by ammonia under mild reaction conditions. The results showed that Rh-PVP was the most active catalyst for reductive amination reaction. Linear, cyclic, and amino alcohols were used as nucleophiles and converted to primary/secondary/tertiary amines. Using this strategy, the synthesis of an industrially important chemical, N-cyclohexyl- 2-pyrrolidone was explored.
Highly selective hydrogenation of aromatic ketones to alcohols in water: effect of PdO and ZrO2
Alsalahi, W.,Trzeciak, A. M.,Tylus, W.
, p. 10386 - 10393 (2021/08/09)
Pd/ZrO2and PdO/ZrO2composites, containing Pd or PdO nanoparticles, were prepared using an original one-step methodology. These nanocomposites catalyze the hydrogenation of acetophenone (AP) at 1 bar and 10 bar of H2in an aqueous solution. Compared to unsupported Pd or PdO nanoparticles, a remarkable increase in their activity was achieved as a result of interaction with zirconia. An unsupported PdO hydrogenated AP mainly to ethylbenzene (EB), while excellent regioselectivity towards 1-phenylethanol (PE) was obtained with PdO/ZrO2and it was preserved during recycling. Similarly, regioselectivity to PE was higher with Pd/ZrO2compared to unsupported Pd NPs. PdO and zirconia resulted in high selectivity to alcohols in the hydrogenation of substituted acetophenones.
Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines
Ben-David, Yehoshoa,Das, Uttam Kumar,Diskin-Posner, Yael,Kar, Sayan,Milstein, David
supporting information, p. 3744 - 3749 (2021/07/09)
We report the first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies. (Figure presented.).
Boosting chemoselective reduction of 4-nitrostyreneviaphotoinduced energetic electrons fromin situformed Cu nanoparticles on carbon dots
Ren, Yuqi,Hao, Caihong,Chang, Qing,Li, Ning,Yang, Jinlong,Hu, Shengliang
supporting information, p. 2938 - 2943 (2021/05/05)
Chemoselective hydrogenation of structurally diverse nitroarenes is a challenging process that often requires precious metal catalysts and proceeds in an organic solvent. Herein, a convenient and stable hybrid nanocatalyst combining carbon dots and copper nanoparticles is developed as an ideal alternative for this transformation. The as-prepared nanocatalyst achieves over 99% selectivity for the formation of 4-aminostyrene at 100% conversion of 4-nitrostyrene in an aqueous solvent under visible light irradiation. Compared with other reported catalysts, our presented catalyst shows more superior hydrogenation selectivity and stability as well as lower material cost. This high efficiency could be originated from the nanocatalyst's ability to synergistically control surface hydrogen species released from ammonia borane and energetic “hot” electrons induced by visible light irradiation for the selective reduction reaction. Compared with other reported catalysts, our presented nanocatalyst is better for the realization of energy-saving chemical processes by introducing solar energy.
Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst
Beller, Matthias,Feng, Lu,Gao, Jie,Jackstell, Ralf,Jagadeesh, Rajenahally V.,Liu, Yuefeng,Ma, Rui
supporting information, p. 18591 - 18598 (2021/06/28)
A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.
Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
supporting information, p. 9029 - 9039 (2021/06/28)
Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
Rhodium-terpyridine Catalyzed Transfer Hydrogenation of Aromatic Nitro Compounds in Water
Liu, Yuxuan,Miao, Wang,Tang, Weijun,Xue, Dong,Xiao, Jianliang,Wang, Chao,Li, Changzhi
supporting information, p. 1725 - 1729 (2021/06/01)
A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h?1, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.
Mechanically Strong Heterogeneous Catalysts via Immobilization of Powderous Catalysts to Porous Plastic Tablets
Li, Tingting,Xu, Bo
supporting information, p. 2673 - 2678 (2021/08/03)
Main observation and conclusion: We describe a practical and general protocol for immobilization of heterogeneous catalysts to mechanically robust porous ultra-high molecular weight polyethylene tablets using inter-facial Lifshitz-van der Waals Interactions. Diverse types of powderous catalysts, including Cu, Pd/C, Pd/Al2O3, Pt/C, and Rh/C have been immobilized successfully. The immobilized catalysts are mechanistically robust towards stirring in solutions, and they worked well in diverse synthetic reactions. The immobilized catalyst tablets are easy to handle and reused. Moreover, the metal leaching of immobilized catalysts was reduced significantly.
