Redox Control in Olefin Polymerization Catalysis by Phosphine–Sulfonate Palladium and Nickel Complexes

Yang, Bangpei; Pang, Wenmin; Chen, Min

doi:10.1002/ejic.201700214

Cited by 17 publications

(7 citation statements)

References 44 publications

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“…The resulting compounds Ia-d and II (Chart ), in which the phosphinoferrocene and sulfonate moieties are connected by an amide linkage, not only were highly hydrophilic but also showed favorable catalytic activity. , In contrast, Erker et al. synthesized a series of 2-phosphinoferrocene-1-sulfonic acids III , , which are indeed closer to the archetypal phosphinosulfonate donors, by utilizing an ortho-lithiation/functionalization approach developed previously for the synthesis of 2-phosphinobenzenesulfonates IV from the corresponding sulfonic acids. , Similar to the studies conducted on IV -type ligands, Pd(II) and Ni(II) complexes with these ferrocene ligands were employed as catalysts for various (co)polymerization reactions. , …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion

2018

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Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO3H (2; fc = ferrocene-1,1′-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO3(HNEt3) (3). Methyl triflate/P(NMe2)3 can be used to convert compound 3 to the stable sulfonate salt Ph2PfcSO3(HNEt3) (4) and Ph2P(Me)fcSO3 (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1′-(diphenylphosphino)-1-bromoferrocene (6; Ph2PfcBr) and trapping of the lithiated intermediate with SO3·NMe3. Reactions of [(LNC)PdX]2 and [(LSC)PdX]2, where X = Cl, AcO, LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC 1, and LSC = 2-[(methylthio-κS)methyl]phenyl-κC 1, with 4 uniformly produced the bis-chelate complexes [(LNC)Pd(Ph2PfcSO3-κ2 O,P)] (7) and [(LSC)Pd(Ph2PfcSO3-κ2 O,P)] (8), respectively. The reaction of [PdCl2(MeCN)2] with 4 afforded the bis(phosphine) complex trans-(Et3NH)2[PdCl2(Ph2PfcSO3-κP)2] (9). Complexes 7–9 were used as defined catalyst precursors for the Suzuki–Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion

2018

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“…The oxidation of Ni17 afforded the cationic complex Ni18 that showed moderate activity towards norbornene polymerization (40 % conversion of NB for 12 h at 80 °C); however, the molecular weight of the resulting polymer has not been reported. [38]…”

Section: Phosphine-sulfonate Ni Complexesmentioning

confidence: 99%

Single‐Component Catalysts for the Vinyl‐Addition Polymerization of Norbornene and its Derivatives

Bermesheva,

Bermeshev

2023

ChemCatChem

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Vinyl‐addition polynorbornenes are versatile templates for the targeted design of high‐performance materials for various applications, such as membrane gas separation, micro‐ and optoelectronics, fuel cells, sensors, catalyst supports, etc. The cornerstone of the syntheses of these compounds is the choice of a catalyst for polymerization. Considering valuable developments in the field of catalysts for vinyl‐addition polymerization (VAP) summarized in previously published reviews, mention should be made that the research efforts were largely focused on two‐ and three‐component catalytic systems that suffer from the need to use a cocatalyst. The aim of this review is to highlight the advances in the design and development of single‐component catalysts for the VAP of norbornenes. Such catalysts are categorized into two main groups, viz., neutral and cationic catalysts. The catalyst structure, the catalytic activity, and the molecular weight characteristics of polymers produced on these catalysts are considered in detail. We believe this article can serve as a guide for developing future catalysts to gain access to new functional materials.

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“…In an attempt to increase the molecular weight of the PE produced, bulky biaryl substituents were introduced to the FcPSO 3 ligand scaffold to obtain 24 and 25 (Scheme a) . A Ni-centered variant, 26 (Scheme a), was also developed in order to expand this class of catalysts to include another active metal center.…”

Section: Redox Controlmentioning

confidence: 99%

“…109 When tested for the polymerization of In an attempt to increase the molecular weight of the PE produced, bulky biaryl substituents were introduced to the FcPSO 3 ligand scaffold to obtain 24 and 25 (Scheme 4a). 110 A Ni-centered variant, 26 (Scheme 4a), was also developed in order to expand this class of catalysts to include another active metal center. When tested for the polymerization of ethylene, 26 was seen to be active but produced low-molecular-weight PE, whereas the oxidized species 26 ox exhibited greatly reduced polymerization activity and produced polymers with even lower molecular weight.…”

Section: Redox Controlmentioning

confidence: 99%

Advances in Polymerizations Modulated by External Stimuli

et al. 2020

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Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, and applications. This is often approached through the development of dynamic catalyst (or initiator) systems that use external stimuli to elicit discrete, site-specific transformations that impact the polymerization. Herein we highlight developments in polymerizations that are modulated by external stimuli, with particular focus on those systems that enable notable changes in kinetics, monomer selectivity, polymer architecture, or tacticity. Examples of external stimuli include chemical oxidants or reductants, light, applied voltage, and mechanical force.

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Redox Control in Olefin Polymerization Catalysis by Phosphine–Sulfonate Palladium and Nickel Complexes

Cited by 17 publications

References 44 publications

Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion

Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion

Single‐Component Catalysts for the Vinyl‐Addition Polymerization of Norbornene and its Derivatives

Advances in Polymerizations Modulated by External Stimuli

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