Vinylic addition poly(norbornene-<i>co</i>-alkenylnorbornenes) synthesized with benzylic palladium catalysts: materials for manifold functionalization

Pérez-Ortega, Ignacio; Albéniz, Ana C.

doi:10.1039/d2py00643j

Cited by 7 publications

(8 citation statements)

References 42 publications

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“…developed cationic Pd complexes with η 3 ‐benzyl‐ligand ( Pd63−Pd68 , Figure 17). [14a,78] This ligand can be readily converted to σ‐benzyl‐ligand to recover the benzene ring aromaticity and create an available coordination site on the Pd center. These complexes proved to be effective catalysts for the polymerization of NB , 1.4 , and alkenyl norbornenes ( 1.5 , Figure 4).…”

Section: Cationic Single‐component Palladium Catalysts For Polymeriza...mentioning

confidence: 99%

“…The nature of metal−C bonds is also essential. For instance, the nature of the allyl group on Pd dramatically affected initiation efficiency and polymer molecular weights [14a,78,81] . Therefore, although no clear guidelines exist for creating a single‐component catalyst with fast initiation and low propagation, systematic tuning of ligands in the metal coordination sphere results in optimal catalyst structural design.…”

Section: Mechanism Of Vinyl‐addition Polymerizationmentioning

confidence: 99%

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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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Section: Cationic Single‐component Palladium Catalysts For Polymeriza...mentioning

confidence: 99%

Section: Mechanism Of Vinyl‐addition Polymerizationmentioning

confidence: 99%

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

Bermesheva,

Bermeshev

2023

ChemCatChem

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“…N–N- and N–O-ligated cationic Pd-complexes of a similar structure were found to be single-component catalysts for VAP of unsubstituted norbornenes. , Chen and co-workers showed that a zwitterionic phospine-sulfonate Ni-complex is a latent catalyst for norbornene polymerization . Recently, Pérez-Ortega and Albeniz reported cationic benzylic Pd-complexes as one-component catalysts for VAP . These catalysts showed good catalytic activity and selectivity in VAP of norbornene and alkenylnorbornenes, however, exhibited low activity in the polymerization of polar norbornenes, and were air-sensitive.…”

Section: Introductionmentioning

confidence: 98%

“…53 Recently, Peŕez-Ortega and Albeniz reported cationic benzylic Pd-complexes as onecomponent catalysts for VAP. 54 These catalysts showed good catalytic activity and selectivity in VAP of norbornene and alkenylnorbornenes, however, exhibited low activity in the polymerization of polar norbornenes, and were air-sensitive. Therefore, to the best of our knowledge, there are no singlecomponent catalysts that combine the good activity, tolerance to functional groups, and resistance to oxygen and air moisture, and are capable of catalyzing living VAP of norbornenes.…”

Section: ■ Introductionmentioning

confidence: 99%

Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes

et al. 2022

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Well-defined single-component and tolerant Ru-, Mo-, and W-catalysts have been earlier developed for ring-opening metathesis polymerization of norbornene and its derivatives. Another way of norbornene polymerization�vinyl-addition polymerization (VAP)�is a more thermodynamically favorable process and gives polymers with saturated and rigid main chains. Single-component catalysts for VAP are required, which combine good activity, tolerance to functional groups, resistance to oxygen, and air moisture and are capable of catalyzing living VAP of norbornenes. Herein, we have shown that cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands ([(NHC)Pd(allyl)L] + A − , where allyl is an allyl group, L = CO, CH 3 CN, CH 2 Cl 2 , and A − = SbF 6 − or BARF − ) are highly efficient single-component catalysts for VAP of both norbornene and various substituted norbornenes. These complexes, being stable in the solid state and in solutions, have exhibited several important features as VAP catalysts. They are capable of catalyzing VAP of norbornenes in air and are tolerant to functional groups. The complexes have shown high catalytic activity and have allowed polymerizing monomers at very low catalyst loadings, as low as 2 ppm. The versatility of [(NHC)Pd(allyl)L] + A − complexes as catalysts of VAP has been demonstrated by successful polymerization of monomers with polar and bulky groups, containing alkyl, vinyl, alkylidene, ether, ester, imide, or organosilicon motifs, affording high-molecular-weight products in good and high yields. Tuning the nature of NHC and allyl ligands in [(NHC)Pd(allyl)L] + A − complexes let perform living VAP, yielding block copolymers.

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“…There are only a few reports about modifications of VAP polynorbornenes. 12,[17][18][19][20][21][22][23][24] in side chains can enhance the gas permeability and gas separation selectivity of VAP polynorbornenes. In addition, the incorporation of appropriate silyl groups into norbornene-and cycloalkane-based polymers is an effective approach to develop degradable and recyclable thermosets.…”

Section: Introductionmentioning

confidence: 99%

Making accessible soluble silicon-containing polynorbornenes: hydrosilylation of vinyl-addition poly(5-vinyl-2-norbornene)

Wozniak,

Bermesheva,

Borisov

et al. 2023

Polym. Chem.

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Vinylic addition poly(norbornene-co-alkenylnorbornenes) synthesized with benzylic palladium catalysts: materials for manifold functionalization

Abstract: The incorporation of functional groups in the skeleton of vinylic addition polynorbornenes (VA-PNBs) is a difficult task due to the reluctant VA homo- and copolymerization of substituted norbornenes. We have...

Cited by 7 publications

References 42 publications

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

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

Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes

Making accessible soluble silicon-containing polynorbornenes: hydrosilylation of vinyl-addition poly(5-vinyl-2-norbornene)

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