Designing highly efficient Rh/CPOL-bp&amp;PPh<sub>3</sub> heterogenous catalysts for hydroformylation of internal and terminal olefins

Li, Cunyao; Xiong, Kai; Li, Yan; Jiang, Miao; Song, Xinshan; Wang, Tao; Chen, Xingkun; Zhan, Zhuang‐Ping; Ding, Yunjie

doi:10.1039/c5cy01655j

Cited by 56 publications

(35 citation statements)

References 53 publications

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“…Incorporation of the sterically hindered Xantphos [4,5-bis(diphenylphosphino)-9,9-dimethylxantene] into the POL-PPh 3 polymer structure leads to some decline in activity of the Rh/CPOL-PPh 3 &Xantphos catalyst during octene-1 hydroformylation (100°С, 6 is divinylbenzene, 7-1,3,5-tri(4-vinylphenyl)benzene, and 8-ethylene glycol dimethacrylate [82]. POLYMERIC HETEROGENEOUS CATALYSTS IN THE HYDROFORMYLATION 1.0 MPa), as compared with Rh/POL-PPh 3 , but regioselectivity increases nearly tenfold (n/iso 9 vs. 0.8) [83]. It is observed that although replacing a tris(4vinylphenyl)phosphine by tris(phenyl)vinylene or divinylbenzene during ligand synthesis makes it possible to obtain catalysts with fairly high regioselectivity (n/iso 5.7 and 3.5, respectively), their resulting activity is even lower, because the phosphorus concentration in the polymer structure is lower too.…”

Section: Doi: 101134/s0965544121010011mentioning

confidence: 99%

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

et al. 2020

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This review deals with heterogeneous hydroformylation catalysts, specifically metal complexes fixed in an organic polymer structure. It describes the main catalyst synthesis methods, provides data on hydroformylation of unsaturated compounds (including asymmetric hydroformylation), and shows how those compounds can be used. The special focus is on the systematization of data on heterogeneous catalysts developed on the basis of porous organic polymers. Due to their porous structure, resistance to organic media and the high concentration of heteroatoms they contain, these materials can be considered promising for developing highly active, selective and stable heterogeneous catalysts for hydroformylation of unsaturated compounds, particularly higher linear olefins.

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Section: Doi: 101134/s0965544121010011mentioning

confidence: 99%

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

et al. 2020

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“…The earliest method was to immobilize the homogeneous active metal species onto commercialized inorganic carriers, but it always leads to metal agglomeration due to the weak interactions between the metal species and the carriers. To bridge the gap between homo‐ and heterogeneous systems, single‐site dispersion of the metal is highly desirable . An important method is to attach the active metals to ligand groups of carriers by coordination bonds .…”

Section: Heterogenization Strategiesmentioning

confidence: 99%

Dual‐Ionically Bound Single‐Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts

et al. 2019

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porous organic polymers (POPs) connected through strong autologous covalent bonds from vinyl-polymerization are emerging as a family of advanced materials advantageous to MOFs, because of a relatively high thermal stability of the skeleton, a hierarchical porosity, as well as the structural diversity. [4] In addition, the ligands [4] or the functional sites [5] in POPs can serve as strong anchoring sites for different metals with great tunability of the metal properties via different preparation methods, being more suitable for cataly sis. It has been believed that the chemical bond between metal species and POPs can be a coordination or an ionic bond, and the latter is generally more stable particularly under harsh reaction conditions. In this context, an effective method to create strong ionic bond is by the immobilization of the ionic active sites onto a new type of POPs with charged skeleton balanced by counterions, coined herein as porous ionic polymers (PIPs). [5] Thanks to the strong bonding and the ionic nature, the resultant single-site metal catalysts can well inherit both the advantages of homo-and heterogeneous processes, i.e., the high activity of the former and the catalyst robustness of the latter. Herein, we first briefly introduce the preparation approaches for porous organic polymers and the corresponding strategies for heterogenization of homogeneous metallic catalysts, and then exemplify a PIP hosted single-site rhodium catalyst (Rh 1 /PIP) for vapor-phase methanol carbonylation, and its excellent performance shows a promising prospect in this exciting field. POPs Polymerized by Vinyl-Based MonomersDifferent synthetic strategies have been developed to prepare POPs. [3,6] The widely used hard or soft-templates are supposed to be removed completely, requiring a highly complicated and energy-consuming procedure. [3] Moreover, the residual metals (Cu, Ni, etc.) as polymerization catalysts for Sonogashira, [7,8] Click, [9] and Yamamoto reactions [10] usually show negative impacts on the catalytic performance of POPs. Contrarily, the polymerization process of vinyl-based monomers is an exception, which can not only avoid the residue of templates and metals, but also offer excellent yields (near 100%) and simple operation. [11] Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh 1 /PIP catalyst, featuring a new active site [Rh(CO)I 3 ] 2− dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO) 2 I 2 ] − in previous studies. Such a u...

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“…Based on the above facts as well as the progress of our long-standing research efforts in hydroformylation [67][68][69][70][71][72][73][74], herein, we introduce a PPh3-based new-generation hydroformylation cage-type ligand (denoted as POC-DICP) as a recyclable and efficient catalyst for long-chain olefin hydroformylation reactions (Fig. 2).…”

Section: Introductionmentioning

confidence: 99%

Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

Wang

Zhang

et al. 2021

Chinese Journal of Catalysis

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Designing highly efficient Rh/CPOL-bp&PPh₃ heterogenous catalysts for hydroformylation of internal and terminal olefins

Abstract: Vinyl functionalized Biphephos ligand, denoted as vinyl biphephos, has been succesfully synthesized.

Cited by 56 publications

References 53 publications

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

Dual‐Ionically Bound Single‐Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts

Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

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Designing highly efficient Rh/CPOL-bp&PPh3 heterogenous catalysts for hydroformylation of internal and terminal olefins

Abstract: Vinyl functionalized Biphephos ligand, denoted as vinyl biphephos, has been succesfully synthesized.

Cited by 56 publications

References 53 publications

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

Dual‐Ionically Bound Single‐Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts

Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

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Designing highly efficient Rh/CPOL-bp&PPh₃ heterogenous catalysts for hydroformylation of internal and terminal olefins