Polymerization of phenylacetylene by cationic acetylacetonate palladium complexes

Suslov, D. S.; Pakhomova, M. V.; Bykov, M. V.; Ushakov, Igor А.; Tkach, V. S.

doi:10.1016/j.catcom.2018.10.010

Cited by 12 publications

(9 citation statements)

References 35 publications

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“…The polymerization of phenylacetylene catalyzed by various metal loaded complexes and attracts more due to its unique properties, for instance, conductivity, humidity sensor, non-linear optical properties, ferromagnetism, and oxygen permeability. [194][195][196][197] Although polymerization of phenylacetylene was not tried by zeolite catalysts. In 2020, Confalonieri et al investigated phenylacetylene polymerization using high-silica mordenite with high pressure for the rst time.…”

Section: Polymerizationmentioning

confidence: 99%

Recent advances in the synthesis and applications of mordenite zeolite – review

et al. 2021

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Section: Polymerizationmentioning

confidence: 99%

Recent advances in the synthesis and applications of mordenite zeolite – review

et al. 2021

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“…The complexes [Pd(acac)(MeCN) 2 ]BF 4 and Pd(cod)Cl 2 were prepared according to published procedures. [39,40,44] 5-methoxycarbonylnorbornene was synthesized in stainless steel autoclave by the Diels-Alder reactions of dicyclopentadiene with methyl acrylate (t = 180 C, 6 h). The crude products were twice distilled over CaH 2 under argon.…”

Section: General Procedures and Materialsmentioning

confidence: 99%

“…[ 31–35 ] However, Pd (II) complexes with bidentate oxadithioether ligands as catalysts for olefin polymerization have only rarely been applied. In previous research, our group reported the synthesis of various cationic acetylacetonate palladium complexes, as well their usage as efficient precursors for the polymerization of norbornene and its derivatives, [ 36–39 ] polymerization of phenylacetylene, [ 40 ] selective dimerization or hydroamination of vinylarenes, [ 39,41 ] and telomerization of butadiene with methanol. [ 42 ]…”

Section: Introductionmentioning

confidence: 99%

“…[31][32][33][34][35] However, Pd (II) complexes with bidentate oxadithioether ligands as catalysts for olefin polymerization have only rarely been applied. In previous research, our group reported the synthesis of various cationic acetylacetonate palladium complexes, as well their usage as efficient precursors for the polymerization of norbornene and its derivatives, [36][37][38][39] polymerization of phenylacetylene, [40] selective dimerization or hydroamination of vinylarenes, [39,41] and telomerization of butadiene with methanol. [42] In this report, we describe the results of the synthesis of novel palladium complexes with SOS-type ligands 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).…”

Section: Introductionmentioning

confidence: 99%

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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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“…The transition-metal-mediated (co)polymerization of arylacetylenes, including 1-substituted and 1,2-disubstituted substrates, in a noncontrolled manner, is well documented. − In distinct contrast, there is a notable dearth of literature reports concerning the living (co)polymerization of arylacetylene monomers and related alkyne substrates such as propargyl esters/amides and arylisocyanides. − With regard to arylacetylenes, Kishimoto et al were the first to report the living polymerization of phenylacetylene (PhC 2 H) employing an in situ generated pentacoordinate rhodium-alkynyl species, Rh(nbd)(CCPh)(PPh 3 ) 2 (nbd = 2,5-norbornadiene). This complex was isolated, and the solid-state structure reported with the species adopting a slightly distorted trigonal bipyramidal geometry.…”

Section: Introductionmentioning

confidence: 99%

(η⁴-Tetrafluorobenzobarrelene)-η¹-((tri-4-fluorophenyl)phosphine)-η¹-(2-phenylphenyl)rhodium(I): A Catalyst for the Living Polymerization of Phenylacetylenes

et al. 2021

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(η4-Tetrafluorobenzobarrelene)-η1-((tri-4-fluorophenyl)phosphine)-η1-(2-phenylphenyl)rhodium(I), Rh(tfb)(biph)(PAr3), was prepared and evaluated as a catalyst in the controlled, stereospecific (co)polymerization of arylacetylenes. Following recrystallization, the complex was characterized by single-crystal X-ray diffraction, elemental analysis, and multinuclear NMR spectroscopy, including 103Rh and 31P-103Rh{1H, 103Rh} heteronuclear multiple quantum coherence (HMQC) experiments. Single-crystal X-ray diffraction indicated that Rh(tfb)(biph)(PAr3) adopts a slightly distorted square-planar geometry consistent with previously reported tetracoordinate rhodium(I)-aryl and -vinyl complexes. 103Rh and 2D 31P-103Rh{1H} HMQC NMR spectroscopy confirmed the purity and stability of the new complex in solution. In the presence of excess P(4-FC6H4)3 as a rate modifier, the Rh(I)-aryl catalyst mediated the homopolymerization of phenylacetylene, PhC2H, in a controlled manner as evidenced from the linearity of the pseudo-first-order kinetic plots, the evolution of molecular weight and dispersity, and the quantitative crossover efficiency in a self-blocking experiment. The broader utility of Rh(tfb)(biph)(PAr3) was demonstrated in the polymerization of a series of functional arylacetylenes, including 4-trifluoromethoxyphenylacetylene and 3,4-dichlorophenylacetylene, as well as in the preparation of well-defined AB diblock copolymers of phenylacetylene with the trifluoromethoxy and dichloro derivatives. Computational studies using density functional theory allowed a quantitative comparison between Rh(tfb)(biph)(PAr3) and the 2,5-norbornadiene (nbd) analogue, Rh(nbd)(biph)(PAr3). Results indicated that the former has a lower HOMO energy compared to the nbd derivative and is consistent with the enhanced π-acidity of the tetrafluorobenzobarrelene ligand species. Calculations similarly indicated that Rh(tfb)(biph)(PAr3) has a slightly higher binding affinity for PhC2H. Finally, we highlight the role the biph aryl ligand plays in stabilizing the rhodium complex through a C–H agostic and η2–π interactions and different steps in the catalyst initiation process.

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Polymerization of phenylacetylene by cationic acetylacetonate palladium complexes

Cited by 12 publications

References 35 publications

Recent advances in the synthesis and applications of mordenite zeolite – review

Recent advances in the synthesis and applications of mordenite zeolite – review

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

(η⁴-Tetrafluorobenzobarrelene)-η¹-((tri-4-fluorophenyl)phosphine)-η¹-(2-phenylphenyl)rhodium(I): A Catalyst for the Living Polymerization of Phenylacetylenes

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Polymerization of phenylacetylene by cationic acetylacetonate palladium complexes

Cited by 12 publications

References 35 publications

Recent advances in the synthesis and applications of mordenite zeolite – review

Recent advances in the synthesis and applications of mordenite zeolite – review

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

(η4-Tetrafluorobenzobarrelene)-η1-((tri-4-fluorophenyl)phosphine)-η1-(2-phenylphenyl)rhodium(I): A Catalyst for the Living Polymerization of Phenylacetylenes

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(η⁴-Tetrafluorobenzobarrelene)-η¹-((tri-4-fluorophenyl)phosphine)-η¹-(2-phenylphenyl)rhodium(I): A Catalyst for the Living Polymerization of Phenylacetylenes