925-54-2Relevant academic research and scientific papers
Methyl-modified cage-type phosphorus ligand and preparation method thereof Preparation method and application thereof
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Paragraph 0075-0084; 0087-0088, (2021/09/15)
The invention discloses a methyl-modified cage-type phosphorus ligand, a preparation method and application thereof, in particular to a synthesis design, wherein methyl is further introduced on a phenyl ring of triphenylphosphine, and a methyl-modified cage-type phosphorus ligand is synthesized, and when a methyl meta-substituted cage-type phosphorus ligand is used as a hydroformylation reaction catalyst the proportion of n-structural aldehyde and isomeric aldehyde is 2.6. TOF-1 The methyl-substituted cage-type phosphorus ligand is excellent in performance, stable in property and recyclable, has excellent substrate applicability in the hydroformylation catalytic reaction, has a good industrial application prospect, and has very important significance in metal organic catalysis.
Catalyst composition containing bidentate phosphine ligand and application thereof
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Paragraph 0068; 0069-0072; 0093-0094, (2021/11/03)
The catalyst composition comprises a bidentate phosphine ligand and a rhodium complex, wherein the skeleton of the bidentate phosphine ligand not only has C. 2 The symmetry and the appropriate rigidity, and the phosphine ligand derived based on the skeleton can provide effective steric hindrance around the catalyst center metal, so that the selectivity of the catalyst can be remarkably improved, the aldehyde yield is not lower 92% when the catalyst combination is applied to the hydroformylation reaction, and the selectivity of n-aldehyde is not lower 90%. In addition, the raw materials olefins with different structures can obtain outstanding reaction rate and normal aldehyde selectivity as compared with the existing catalyst systems, and can be suitable for the hydroformylation reaction of more types of olefins.
Intermetallic Nanocatalyst for Highly Active Heterogeneous Hydroformylation
Chen, Minda,Gupta, Geet,Ordonez, Claudio W.,Lamkins, Andrew R.,Ward, Charles J.,Abolafia, Celia A.,Zhang, Biying,Roling, Luke T.,Huang, Wenyu
supporting information, p. 20907 - 20915 (2021/12/14)
Hydroformylation is an imperative chemical process traditionally catalyzed by homogeneous catalysts. Designing a heterogeneous catalyst with high activity and selectivity in hydroformylation is challenging but essential to allow the convenient separation and recycling of precious catalysts. Here, we report the development of an outstanding catalyst for efficient heterogeneous hydroformylation, RhZn intermetallic nanoparticles. In the hydroformylation of styrene, it shows three times higher turnover frequency (3090 h-1) compared to the benchmark homogeneous Wilkinson's catalyst (966 h-1), as well as a high chemoselectivity toward aldehyde products. RhZn is active for a variety of olefin substrates and can be recycled without a significant loss of activity. Density functional theory calculations show that the RhZn surfaces reduce the binding strength of reaction intermediates and have lower hydroformylation activation energy barriers compared to pure Rh(111), leading to more favorable reaction energetics on RhZn. The calculations also predict potential catalyst design strategies to achieve high regioselectivity.
The invention relates to a bidentate phosphine ligand and a preparation method thereof. Application
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Paragraph 0054-0061, (2021/11/03)
The invention discloses a bidentate phosphine ligand and a preparation method and application thereof, and a ligand skeleton adopted by the bidentate phosphine ligand not only has C. 2 The phosphine ligand derived from the skeleton can provide effective steric hindrance around the catalyst center metal, so that selectivity of the catalyst can be remarkably improved, and furthermore, the phosphine ligand skeleton is simple in synthesis route, easy to obtain in large quantities, capable of effectively improving production efficiency and reducing industrial production cost.
Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information, p. 8040 - 8046 (2021/11/01)
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
Rh-catalyzed highly regioselective hydroformylation to linear aldehydes by employing porous organic polymer as a ligand
Wang, Zhaozhan,Yang, Yong
, p. 29263 - 29267 (2020/10/06)
In this work, we developed a new structural porous organic polymer containing biphosphoramidite unit, which can be used as a solid bidentate phosphorous ligand for rhodium-catalyzed solvent-free higher olefins hydroformylation. The resultant catalyst demonstrated unprecedently high regioselectivity to linear aldehydes and could be readily recovered for successive reuses with good stability in both catalytic activity and regioselectivity. This journal is
Highly uniform Rh nanoparticles supported on boron doped g-C3N4 as a highly efficient and recyclable catalyst for heterogeneous hydroformylation of alkenes
Shi, Yukun,Ji, Gang,Hu, Qiqige,Lu, Yang,Hu, Xiaojing,Zhu, Baolin,Huang, Weiping
supporting information, p. 20 - 23 (2019/12/26)
A series of boron doped g-C3N4 supported rhodium nanoparticle catalysts has been synthesized for the first time and exhibited excellent catalytic activity and easy recycling properties in the hydroformylation of styrene due to the boron doping, which modified the delocalized conjugated π structure of g-C3N4 and increased the adsorption and dispersion of Rh nanoparticles.
Organic Ligand-Free Hydroformylation with Rh Particles as Catalyst?
Liu, Shujuan,Dai, Xingchao,Wang, Hongli,Wang, Xinzhi,Shi, Feng
supporting information, p. 139 - 143 (2020/01/03)
An efficient and organic ligand-free heterogeneous catalytic system for hydroformylation of olefins is highly desirable for both academy and industry. In this study, simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in the absence of organic ligand. The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic olefins, affording the desired aldehydes in good yields. Taking the hydroformylation of ethylene as an example, 86% yield of propanal and TOF of 200 h–1 were obtained, which was superior to the reported homogeneous catalytic systems. In addition, the catalyst could be reused five times without loss of activity under identical reaction conditions, and the Rh leaching was negligible after each cycle.
Highly active cationic cobalt(II) hydroformylation catalysts
Carpenter, Alex E.,Hood, Drew M.,Johnson, Ryan A.,Stanley, George G.,Vinyard, David J.,Younker, Jarod M.
, p. 542 - 548 (2020/02/13)
The cobalt complexes HCo(CO)4 and HCo(CO)3(PR3) were the original industrial catalysts used for the hydroformylation of alkenes through reaction with hydrogen and carbon monoxide to produce aldehydes. More recent and expensive rhodium-phosphine catalysts are hundreds of times more active and operate under considerably lower pressures. Cationic cobalt(II) bisphosphine hydrido-carbonyl catalysts that are far more active than traditional neutral cobalt(I) catalysts and approach rhodium catalysts in activity are reported here. These catalysts have low linear-to-branched (L:B) regioselectivity for simple linear alkenes. However, owing to their high alkene isomerization activity and increased steric effects due to the bisphosphine ligand, they have high L:B selectivities for internal alkenes with alkyl branches. These catalysts exhibit long lifetimes and substantial resistance to degradation reactions.
Triphenylphosphine-Based Covalent Organic Frameworks and Heterogeneous Rh-P-COFs Catalysts
Liu, Yubing,Dikhtiarenko, Alla,Xu, Naizhang,Sun, Jiawei,Tang, Jie,Wang, Kaiqiang,Xu, Bolian,Tong, Qing,Heeres, Hero Jan,He, Songbo,Gascon, Jorge,Fan, Yining
supporting information, p. 12134 - 12139 (2020/09/01)
The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine-based COF family, but also demonstrates their application in immobilizing homogeneous metal-based (e.g., Rh-phosphine) catalysts for application in heterogeneous catalysis.
