Enhancing Thermal Stability in Aminopyridine Iron(II)-Catalyzed Polymerization of Conjugated Dienes

Jing, Chuyang; Wang, Liang; Zhu, Guangqian; Hou, Hongbin; Zhou, Li; Wang, Qinggang

doi:10.1021/acs.organomet.0c00591

Cited by 25 publications

(18 citation statements)

References 54 publications

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“…Well-defined aminopyridine iron(II) complexes with a tertiary amine moiety have been prepared and used in association with MAO for the polymerization of isoprene, showing excellent activities (up to 2340 kg polyisoprene (mol Fe) −1 h –1 ) and giving polymers with a mixed cis -1,4/ trans -1,4 structure (Figure ). The same systems were also able to polymerize the biobased myrcene and β-farnesene providing high molecular weight polymers …”

Section: Catalysts Based On Transition Metal and Lanthanide Complexes...mentioning

confidence: 99%

Dienes Polymerization: Where We Are and What Lies Ahead

Ricci¹,

Pampaloni

Sommazzi

et al. 2021

Macromolecules

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Recently, the research activity in the field of the stereospecific polymerization of conjugated dienes has focused on the use of catalysts based on organometallic complexes having a well-defined structure and containing ligands of various types (e.g., phosphines, bis-imines, and pyridylimines), since it has been observed that the nature of the ligand, as expected on the basis of the diene polymerization mechanism proposed several years ago by Porri, is able to exert a strong influence on the polymerization regioand stereoselectivity, on the polymer molecular weights and their distribution, and in some cases to impart a living feature to the catalysts themselves. In this Perspective we highlight the most recent results obtained in this field and discuss possible future developments in this area.

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Section: Catalysts Based On Transition Metal and Lanthanide Complexes...mentioning

confidence: 99%

Dienes Polymerization: Where We Are and What Lies Ahead

Ricci¹,

Pampaloni

Sommazzi

et al. 2021

Macromolecules

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“…Most of the work carried out concerned, in particular, cobalt-based catalysts and, to a lesser extent, chromium, vanadium, titanium, zirconium, and lanthanide (neodymium in particular) derivatives . Recently, however, there has been a considerable rediscovery of iron-based systems, − which have proved to be extremely active, selective, in some cases with living characteristics, and capable of polymerizing different types of conjugated dienes (e.g., 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 3-methyl-1,3-pentadiene), affording stereoregular polymers having different structures depending on the monomer employed. − This last feature specifically allowed us to improve and confirm our knowledge on the conjugated diene polymerization mechanism …”

Section: Introductionmentioning

confidence: 99%

Highly Stereoregular 1,3-Butadiene and Isoprene Polymers through Monoalkyl-N-Aryl-Substituted Iminopyridine Iron Complex-Based Catalysts: Synthesis and Characterization

Ricci¹,

Leone²,

Zanchin³

et al. 2021

Macromolecules

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Some novel monoalkyl-N-aryl-substituted iminopyridine iron chloride complexes, differing in the nature of the substituent at the iminic carbon and at the ortho position of the aryl ring, were synthesized and characterized. For one of them, single crystals were obtained, which allowed for the determination of its crystalline structure, in which the iron center is coordinated to the chlorides and to the two nitrogen atoms of the ligand. The coordination around iron is distorted tetrahedral, a coordination mode rarely identified for FeCl2 adducts with bidentate nitrogen ligands. All the complexes were used, in combination with methylaluminoxane, for the polymerization of 1,3-butadiene and isoprene, providing syndiotactic 1,2 poly(1,3-butadiene)s and poly(isoprene)s with a predominantly cis-1,4/3,4 alternating structure, in which short cis-1,4 sequences of three or five units, whose length depends on the nature of the ligand on the iron atom, are present. A detailed NMR characterization (1H-, 13C-, and 2D experiments) of the resultant poly(isoprene)s is reported, and a tentative scheme for the formation of the novel isoprene polymers is proposed.

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“…[60] In particular, complex 33 ( More recently, Wang and co-authors introduced for M and F polymerization a library of novel aminopyridine iron(II) chloride catalysts 35-38, bearing different alkyl substituents (methyl, ethyl, benzyl, and isopropyl groups) on the amine moiety. [61] The catalytic activity was both influenced by the steric hindrance of the ligand and the Lewis acidity of the metal center. The isopropyl group of 38 appears to show the best compromise, facilitating coordination and insertion of monomers and providing the higher activity (13.7 kg mol Fe À 1 h À 1 in the case of PF).…”

Section: Ironmentioning

confidence: 99%

Stereoregular Polymerization of Acyclic Terpenes

2021

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The growing environmental pollution and the expected depleting of fossil resources have sparked interest in recent years for polymers obtained from monomers originating from renewable sources. Furthermore, nature can provide a variety of building blocks with special structural features (e. g. side groups or stereo-elements) that cannot be obtained so easily via fossilbased pathways. In this context, terpenes are widespread natural compounds coming from non-food crops, present in a large variety of structures, and ready to use as monomers with or without further modifications. The present review aims to provide an overview of how chemists can stereospecifically polymerize terpenes, particularly the acyclic ones like myrcene, ocimene, and farnesene, using different metal catalyst systems in coordination-insertion polymerization. Attention is also paid to their copolymers, which have recently been disclosed, and to the possible applications of these bio-based materials in various industrial sectors such as in the field of elastomers.

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Enhancing Thermal Stability in Aminopyridine Iron(II)-Catalyzed Polymerization of Conjugated Dienes

Cited by 25 publications

References 54 publications

Dienes Polymerization: Where We Are and What Lies Ahead

Dienes Polymerization: Where We Are and What Lies Ahead

Highly Stereoregular 1,3-Butadiene and Isoprene Polymers through Monoalkyl-N-Aryl-Substituted Iminopyridine Iron Complex-Based Catalysts: Synthesis and Characterization

Stereoregular Polymerization of Acyclic Terpenes

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