Norbornene Addition Polymerization with Catalysts Based on Transition Metal Compounds: 2008–2018

Suslov, D. S.; Bykov, M. V.; Kravchenko, O. V.

doi:10.1134/s181123821901017x

Cited by 22 publications

(15 citation statements)

References 202 publications

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“…Addition polynorbornene (PNB) has received considerable attention due to its dielectric and mechanical properties for technical application as an interlevel dielectric in microelectronics applications. [76][77][78][79] Catalyst systems based on palladium and nickel complexes in different oxidation states exhibit high activity (usually in the range of 10 5 -10 7 g NB mol À1 cat h À1 ) in the addition polymerization of NB. [76][77][78][79] A variety of palladium complexes have been reported to be active for the polymerization of norbornene, [76,79] but the application of oxadithioether-chelated palladium complexes in this reaction is not known to date.…”

Section: Catalytic Studiesmentioning

confidence: 99%

“…[76][77][78][79] Catalyst systems based on palladium and nickel complexes in different oxidation states exhibit high activity (usually in the range of 10 5 -10 7 g NB mol À1 cat h À1 ) in the addition polymerization of NB. [76][77][78][79] A variety of palladium complexes have been reported to be active for the polymerization of norbornene, [76,79] but the application of oxadithioether-chelated palladium complexes in this reaction is not known to date. We studied the polymerization of norbornene (Scheme 3) with chlorido palladium complexes (1a-8a) in the presence of typical Ziegler-Natta alkylating cocatalyst (Al i Bu 2 Cl).…”

Section: Catalytic Studiesmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Suslov

Abramov

Babenko

et al. 2021

Applied Organom Chemis

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The Pd (II) complexes trans-[PdCl 2 (μ-L)] 2 and [Pd(acac)(L)][BF 4 ] (L = RS (CH 2 ) 2 O(CH 2 ) 2 SR, R = Me, Et, n Pr, i Pr, n Bu, i Bu, n-hexyl, benzyl) were obtained through the reaction of Pd(cod)Cl 2 or [Pd(acac)(MeCN) 2 ][BF 4 ] with one equivalent of oxadithioether (L). The structural features of these complexes were analyzed by nuclear magnetic resonance (NMR) and Fouriertransform infrared spectroscopy (FTIR), as well as electrospray ionisation mass spectrometry and density functional theory calculations. The complexes diμ-(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 )-bis[trans-dichloropalladium (II)] and (acetylacetonate-κ 2 O,O 0 )(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S, S 0 )palladium (II) tetrafluoroborate were characterized by X-ray diffractometry. The X-ray structures of each complex indicate an axial M-O interaction formed by the endodentate conformation of the oxadithioether ligand. Palladium (II) dichloride complexes with oxadithioethers were demonstrated to have a 16-membered dinuclear structure with a trans-configured S 2 PdCl 2 fragment. In the case of cationic palladium acetylacetonate complexes, only mononuclear complexes with a cis configuration of the oxadithioether fragment were observed. Variable temperature 1 H and 13 C NMR studies of the complexes demonstrate dynamic bonding of the oxadithioether ligands consistent with the presence of diastereoisomers that differ in the orientation of the S-R groups along with both endodentate and exodentate bonding modes in solution. FTIR studies of the complexes indicate the presence of isomers in the solid state. The palladium catalyst precursors trans-[PdCl 2 (μ-L)] 2 and [Pd (acac)(L)][BF 4 ] were found to be active in the addition polymerization of norbornene. In the presence of cocatalysts, such as diisobutylaluminum chloride and boron trifluoride etherate, Pd (II) complexes exhibited activities in the range of 10 5 to 10 7 g of polymer (mol of Pd) À1 h À1 . The catalyst systems

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Section: Catalytic Studiesmentioning

confidence: 99%

Section: Catalytic Studiesmentioning

confidence: 99%

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Suslov

Abramov

Babenko

et al. 2021

Applied Organom Chemis

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“…Considering different cycloolefins, norbornenes attract the attention of researchers as model monomers for catalytic activity tests and as building blocks for new polymeric materials owing to the diversity of norbornene chemistry, their availability, and the high reactivity of norbornene double bonds. A huge number of two- and three-component systems based on transition metal salts which are the most widely used catalysts for VAP of norbornenes ,,,,− have been developed. However, these systems have a number of known disadvantages when compared to single-component catalysts. ,, At the same time, single-component catalysts for VAP of norbornenes are rare, and single-component catalysts capable of catalyzing living VAP of norbornenes are scarce.…”

Section: Introductionmentioning

confidence: 99%

“…Later related complexes were developed. 26 Such complexes catalyzed polymerization in a well-behaved manner and exhibited tolerance to some functional groups, but these catalysts showed moderate catalytic activity and were sensitive to air. Later Goodall et al reported that complexes such as [(allyl)M(COD)] + PF 6 − (M = Ni, Pd; COD = cyclooctadiene-1,5) are singlecomponent catalysts for 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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“…This feature allows involvement in polymerization monomers, bearing two, three, or four substituents, which is often impossible for a polymerization of most olefins. Second, there are at least two ways for polymerization of cycloalkenes (ring-opening metathesis polymerization and vinyl (addition) polymerization [1][2][3][4][5]), which give polymers with different structure and properties. Third, owing to well-developed organic tools, such as cycloaddition reactions [6,7], a huge number of cycloalkenes can be prepared, and this provides an opportunity to perform systematic structure-property investigations.…”

Section: Introductionmentioning

confidence: 99%

Gas-Transport and the Dielectric Properties of Metathesis Polymer from the Ester of exo-5-Norbornenecarboxylic Acid and 1,1′-Bi-2-naphthol

et al. 2022

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Polymers from norbornenes are of interest for applications in opto- and microelectronic (low dielectric materials, photoresists, OLEDs). Norbornenes with ester motifs are among the most readily available norbornene derivatives. However, little is known about dielectric properties and the gas-transport of polynorbornenes from such monomers. Herein, we synthesized a new metathesis polymer from exo-5-norbornenecarboxylic acid and 1,1′-bi-2-naphthol. The designed monomer was obtained via a two-step procedure in a good yield. This norbornene derivative with a rigid and a bulky binaphthyl group was successfully polymerized over the 1st generation Grubbs catalyst, affording high-molecular-weight products (Mw ≤ 1.5·106) in yields of 94–98%. The polymer is amorphous and glassy (Tg = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer. The selectivity of polyNBi was higher than that of polyNB. Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB). Therefore, the molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics. Further tuning of the gas separation efficiency can be achieved by attaching an appropriate substituent to the ester and aryl group.

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Norbornene Addition Polymerization with Catalysts Based on Transition Metal Compounds: 2008–2018

Cited by 22 publications

References 202 publications

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

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

Gas-Transport and the Dielectric Properties of Metathesis Polymer from the Ester of exo-5-Norbornenecarboxylic Acid and 1,1′-Bi-2-naphthol

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