Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

García-Suárez, Eduardo J.; Godard, Cyril; Ruiz, Aurora; Claver, Carmen

doi:10.1002/ejic.200700024

Cited by 71 publications

(33 citation statements)

References 107 publications

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“…During the last few decades palladium(II) complexes with chelating nitrogen-donor ligands (N-N) have been widely investigated as homogeneous catalysts for (co)polymerization reactions. [1] Considerable attention has been addressed to the copolymerization of carbon monoxide with vinyl arenes to yield perfectly alternating polyketones [2][3][4][5][6][7][8] and, more recently, to the copolymerization of ethylene with polar vinyl monomers, like acrylic esters, leading to functionalized polyolefins (Scheme 1). [9][10][11][12][13][14][15][16][17] These two reactions share the N-N-based precatalysts that are organometallic, monocationic, monochelated Pd II complexes of general formula [Pd(CH 3 )(CH 3 CN)(N-N)][X] (X = PF 6 À , BArF= B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 À ).…”

Section: Introductionmentioning

confidence: 99%

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

et al. 2014

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The catalytic CO/styrene and ethylene/methyl acrylate copolymerizations are compared for the first time by applying the same precatalysts. With this aim, PdII neutral, [Pd(CH3)Cl(N–N)], and monocationic, [Pd(CH3)(L)(N–N)][PF6] (L=CH3CN, DMSO), complexes with 1-naphthyl- and 2-naphthyl-substitued α-diimines with both an acenaphthene and a diazabutadiene skeleton as chelating nitrogen-donor ligands (N–N) have been studied. In the case of the complexes with the 1-naphthyl-substituted ligands, syn and anti isomers are found both in solid state and in solution. All the monocationic complexes generate active catalysts for the CO/styrene copolymerization leading to atactic or isotactic/atactic stereoblock copolymers depending on the ligand bonded to palladium. Instead, in the case of the ethylene/methyl acrylate copolymerization only the complexes with the 1-naphthyl-substituted ligands generate catalysts for this reaction

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Section: Introductionmentioning

confidence: 99%

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

et al. 2014

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“…The catalyst activity and copolymer stereoregularity are amongst the best reported for CO/TBS copolymerization under similar conditons (no use of trifluoroethanol,25 room temperature), and the molecular weight of the copolymer produced under these conditions by 3 ⋅ C 2 (118×10 3 g mol −1 ) is the highest reported to date 14. 15…”

Section: Methodsmentioning

confidence: 71%

Templated Encapsulation of Pyridyl‐Bian Palladium Complexes: Tunable Catalysts for CO/4‐tert‐Butylstyrene Copolymerization

Flapper¹,

Reek²

2007

Angew Chem Int Ed

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Dedicated to Professor David N. Reinhoudt on the occasion of his 65th birthdayThe properties of transition-metal catalysts are largely dominated by the direct environment around the metal center, and traditionally the steric environment has been adjusted by ligands that are coordinated to the metal center. Enzymes create a suitable cavity around an active site to provide the required steric and electronic environment. This has inspired scientists to create nanosized capsules to facilitate stochiometric and catalytic transformations in synthetic cavities, resulting in unique conversions. [1,2] We have been particularly interested in the encapsulation of transition-metal complexes and the effect on the catalytic performance, and we therefore developed a template-ligandassisted approach as a new strategy to make such complexes generally accessible. [3][4][5][6][7] For example, trispyridylphosphine templates and rhodium complexes thereof can be encapsulated by three zinc(II) porphyrin units through nitrogen-zinc coordination. Rhodium encapsulation results in a remarkable change in catalyst selectivity; in the hydroformylation of 1-octene, [3,4] mainly branched aldehydes are formed; for internal octenes, such as 3-octene, regioselective reactions were also accomplished.[7] The approach was extended to templated ligand assemblies based on zinc(II) salphen complexes (salphen = N,N'-bis(salicylidene)-o-phenylenediamine dianion), which are more accessible building blocks and easier to vary structurally.[5] Scheme 1 shows an example of the efficient ligand encapsulation by zinc(II) salphen complexes and also displays the solid-state structure of the three-to-one assembly that was also shown to exist in solution. [6] So far, templated encapsulation has been based on the complementary use of donor atoms; zinc has a low affinity for phosphine ligands, and the monopyridyl ligands have lower affinity for the catalytically active metals used to date. Herein, we demonstrate that similar assemblies can be based on template ligands that only have nitrogen donor atoms, in which case selective coordination is based on steric differences. The palladium complexes thus obtained are active in the CO/4-tert-butylstyrene copolymerization, and the activity and selectivity strongly depend on the building blocks used for the ligand assembly.With the 3-pyridyl-bian ligand (mPy-bian (1), see Scheme 2), encapsulation [8] takes place through the pyridyl groups, whereas in the presence of zinc(II) salphen building blocks, palladium complexes are coordinated to the bis-imine Scheme 1. Formation of a three-to-one assembly as a typical example of the template-ligand approach to encapsulation. The structure depicts the three-to-one assembly; P orange, Zn light blue, O red, N blue, Cl yellow, C green, H gray.Scheme 2. Formation of an encapsulated neutral palladium complex and the PM3-TM optimized structure of the assembly with salphen C from Scheme 4; Pd, Zn, Cl all purple, O red, N blue, C green, H gray.

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“…These features make COP an attractive platform for producing sustainable polymers for a variety of applications . Among the COPs, CO–olefin copolymerization is well‐studied, while the COPs of heteroatom‐containing comonomers (for example, epoxides, aziridines, imines, etc.) only experienced a modest amount of research interest …”

Section: Methodsmentioning

confidence: 99%

Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers

Dai

Peng

et al. 2018

Angew Chem Int Ed

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Zwitterionic structure is necessary for Ni complexes to catalyze carbonylative polymerization (COP) of cyclic ethers. The cationic charge at the Ni center imparts sufficient electrophilicity to the Ni-acyl bond for it to react with cyclic ethers to give an acyl-cyclic ether oxonium intermediate, while the ligand-centered anionic charge ensures that the resultant oxonium cation is ion-paired with the Ni nucleophile. The current catalysts give non-alternating copolymers of carbon monoxide and cyclic ethers and are the most effective when both ethylene oxide and tetrahydrofuran are present as the cyclic ether monomers.

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Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

Cited by 71 publications

References 107 publications

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Templated Encapsulation of Pyridyl‐Bian Palladium Complexes: Tunable Catalysts for CO/4‐tert‐Butylstyrene Copolymerization

Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers

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