Polymerization Catalysts Take a Walk on the Wild Side

Jarrett-Wilkins, Charles N.; Pollit, Adam A.; Seferos, Dwight S.

doi:10.1016/j.trechm.2020.03.004

Cited by 10 publications

(9 citation statements)

References 94 publications

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“…This phenomenon might be attributed to yttrium (Y) species being bonded to or oxidized by a more electronegative and electronic structure of thiophene rings in repeated polymer backbone units. [ 41 ] In contrast to YVO, V 2p spectra of PEDOT@YVO composite manifest a low valence state at a lower binding energy region. The V 2p 3/2 peak can be deconvoluted into two peaks, speculating mixed vanadium cations (i.e., V 5+ or V 4+ ) tend to shift to 515.3 eV.…”

Section: Resultsmentioning

confidence: 99%

Yttrium Vanadium Oxide–Poly(3,4‐ethylenedioxythiophene) Composite Cathode Material for Aqueous Zinc‐Ion Batteries

Kumankuma-Sarpong

Guo

2021

Small Methods

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The development of metal ion‐intercalated active materials for excellent electrochemical performance in rechargeable aqueous zinc‐ion batteries (AZIBs) is challenging. The structure instability and intrinsic electrostatic repulsion of the lattice framework cause structural breakdown and low‐rate performance. In response to these problems, yttrium vanadium oxide–poly(3,4‐ethylenedioxythiophene) (PEDOT@YVO) composite is reported as stable cathode material for AZIBs. The introduction of PEDOT in YVO nanorods improves the crystalline structure with an enlarged interplanar lattice spacing of 3.4 Å. The PEDOT@YVO composite electrode demonstrates effective electric conductivity and a higher initial specific capacity of 308.5 mAh g−1 than that (125.5 mAh g−1) of the pure YVO at 0.2 C rate. It also features a long‐term stable discharge–charge cycle performance of 4000 cycles with a capacity retention of 79.2% at 1C rate, better than YVO (29.4 mAh g−1). The oxygen vacancies and improved electrical conductivity of the composite account for the invigorated electrochemical performance. Consequently, this work reveals another avenue for constructing unique electrodes to enhance the electrochemical properties of AZIBs.

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Section: Resultsmentioning

confidence: 99%

Yttrium Vanadium Oxide–Poly(3,4‐ethylenedioxythiophene) Composite Cathode Material for Aqueous Zinc‐Ion Batteries

Kumankuma-Sarpong

Guo

2021

Small Methods

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“…One relies on catalyst association with the propagating polymer chain via a metal-p complex, which has been termed catalyst transfer polymerization (CTP). [16][17][18] The other is dictated by reactivity differences rather than an associative intermediate, 19,20 where the dissociated catalyst preferentially reacts with the C-Br bond at the polymer terminus instead of the counterpart on a organometallic monomer, reminiscent of the living synthesis of polyamide. 17,21 In this review, we will summarize the recent progress of Kumada, Negishi, Murahashi, Suzuki-Miyaura, and direct arylation polymerizations, representing the best routes to welldefined, high molecular weight (MW) CPs containing furan, thiophene, selenophene, and tellurophene.…”

Section: Polymerization Methodsmentioning

confidence: 99%

“…In recent years, the hypothesis that Ni(0) is able to ring-walk over the conjugated polymer backbone has become commonly accepted since many experiments have provided indirect evidence for it. 16,37 For further reading on this topic, please refer to other articles and reviews. 16,[38][39][40] Kumada CTP and Negishi CTP have been employed for many different monomers (Fig.…”

Section: Kumada and Negishi Polymerizationsmentioning

confidence: 99%

Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene

Lotocki

et al. 2022

Chem. Soc. Rev.

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“…2 , path A). The ability of catalysts to ring walk is an important mechanistic feature in chain transfer polymerizations (CTP) enabling access to polymers with controlled polydispersities 19 – 22 . Consequently, significant effort has been devoted to discovering nickel and, more recently, palladium catalysts that promote efficient CTPs for Kumada and Suzuki-type polymerizations 20 .…”

Section: Introductionmentioning

confidence: 99%

“…Despite the importance of the BHA 23 , 24 and polytriarylamines 25 , studies probing ring walking behavior under BHA conditions have remained virtually absent from the literature 26 , 27 . Furthermore, evidence for the mechanistic phenomenon of ring walking itself has remained largely circumstantial 19 – 22 . Mechanistic studies of CTPs have revealed turnover-limiting steps downstream of oxidative addition, precluding the ability to directly observe the short-lived catalyst pi complex 28 – 30 .…”

Section: Introductionmentioning

confidence: 99%

Ring walking as a regioselectivity control element in Pd-catalyzed C-N cross-coupling

et al. 2022

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Ring walking is an important mechanistic phenomenon leveraged in many catalytic C-C bond forming reactions. However, ring walking has been scarcely studied under Buchwald-Hartwig amination conditions despite the importance of such transformations. An in-depth mechanistic study of the Buchwald-Hartwig amination is presented focussing on ligand effects on ring walking behavior. The ability of palladium catalysts to promote or inhibit ring walking is strongly influenced by the chelating nature of the ligand. In stark contrast, the resting state of the catalyst had no impact on ring walking behavior. Furthermore, the complexity of the targeted system enabled the differentiation between catalysts which undergo ring walking versus diffusion-controlled coupling. The insights gained in this study were leveraged to achieve desymmetrization of a tetrabrominated precursor. A small library of asymmetric 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9’spirobifluorene (SpiroOMeTAD) derivatives were successfully synthesized using this strategy highlighting the ease with which libraries of these compounds can be accessed for screening.

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Polymerization Catalysts Take a Walk on the Wild Side

Cited by 10 publications

References 94 publications

Yttrium Vanadium Oxide–Poly(3,4‐ethylenedioxythiophene) Composite Cathode Material for Aqueous Zinc‐Ion Batteries

Yttrium Vanadium Oxide–Poly(3,4‐ethylenedioxythiophene) Composite Cathode Material for Aqueous Zinc‐Ion Batteries

Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene

Ring walking as a regioselectivity control element in Pd-catalyzed C-N cross-coupling

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