Ethylene Polymerization with a Highly Active and Long-Lifetime Macrocycle Trinuclear 2,6-Bis(imino)pyridyliron

Liu, Jingyu; Li, Yuesheng; Liu, Jingyao; Li, Ze-Sheng

doi:10.1021/ma047685y

Cited by 61 publications

(38 citation statements)

References 30 publications

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“…These ligands are then metallated using an appropriate Fe or Co metal precursor, such as Fe and Co halides . In similarity to the Ni‐ and Pd‐based catalysts described above, researchers discovered that bulky ligand frameworks are required to prevent premature chain transfer events and to access high‐molecular‐weight polymers . Catalysts 3a and 3b are prototypical examples of these bis(imino)pyridine catalysts and were shown to polymerize ethylene at temperatures as high as 90 and 125 °C, producing polymers with modest molecular weights (9–17.4 kg mol –1 ).…”

Section: Thermally Robust Fe‐ and Co‐based Catalystsmentioning

confidence: 99%

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Mitchell

Long

2018

Polymer International

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Olefin polymerization catalysts employing late transition metals, such as Ni, Pd, Fe and Co, have been heavily investigated since their discovery in the mid‐1990s. Despite the advantages and appeal these catalysts have displayed in academic research, their implementation in industry has remained restricted due to a variety of limitations and drawbacks. One specific limitation is the relative thermal instability of most late transition metal olefin polymerization catalysts at the temperatures commonly utilized for industrial polymerizations. This review focuses on the development of Ni‐, Pd‐, Fe‐ and Co‐based olefin polymerization catalysts that display increased thermal stability at super‐ambient reaction temperatures. These advances in thermal stability have been realized using a variety of ligand modifications, and their polymerization activities and thermal stability are summarized herein. Lastly, a brief outlook on the future of thermally stable, late transition metal olefin polymerization catalysts is provided. © 2018 Society of Chemical Industry

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Section: Thermally Robust Fe‐ and Co‐based Catalystsmentioning

confidence: 99%

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Mitchell

Long

2018

Polymer International

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“…Trimetallic Fe complexes with cyclic bis(imino)pyridine ligands [225] and tetranuclear Ni catalyst based on linear oligodiimine ligand [226] show higher catalytic activity and/or longer lifetime than the mononuclear complex, although the cooperation mechanism of the metal centers is not clear. Tetra-, octa-and hexadecanuclear pyridylimine Ni complexes having similar dendritic ligands with 1st, 2nd and 3rd generations (12d) are reported [227].…”

Section: Multimetallic Catalystsmentioning

confidence: 99%

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

Takeuchi

2014

Organometallic Reactions and Polymerization

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Diimine Pd and Ni complexes catalyze the polymerization of ethylene, propylene, and a-olefins. The reaction involves isomerization of the growing terminal (chain walking) and, as its result, produces highly branched polyethylene and poy(a-olefin)s having a smaller number of the alkyl substituents than expected from the monomer structure. Ni complexes with salicylaldimine or iminocarboxamide ligands and Pd complexes with phosphinesulfonate ligands are used as single component catalysts for ethylene polymerization. Especially, the latter catalysts show tolerance towards polar functional groups and promote copolymerization of ethylene with wide varieties of polar monomers. The Pd and Ni complexes are able to catalyze ethylene polymerization in aqueous media to yield polyethylene particles. Fe and Co complexes with bis(imino)pyridine ligands show high catalytic activity for ethylene polymerization to yield linear polyethylene. Complexes of the metals such as Rh, Ir, Ru, and Ag were revealed to become catalytically active by proper design of the ligand. Not only monometallic complexes but also bimetallic or multimetallic complexes are used for ethylene polymerization. Late transition metal complexes catalyze selective cyclopolymerization of non-conjugated dienes and trienes to afford the polymers with cycloalkane groups with controlled stereochemistry.

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“…6 Therefore it attracts special attention to emulate these enzymes to build functionalized molecules capable of catalyzing the polymerization reactions in a specific way to attain specified products. 7,8 Recently, considerable interest has been focused on combined catalytic systems in general chemical processes, and extensive investigations have also been drawn into their use in ethylene reactivity. 9 Respect to the preference toward iron and cobalt catalysts for use in ethylene reaction, the most common model in building the combined catalytic systems is by coupling multi-bis(imino)-pyridyl or -(imino)pyridyl metal (iron or cobalt) moieties into a molecule, 8,10,11 based on expectations that their catalytic behavior may significantly differ from those simple derivatives.…”

Section: Introductionmentioning

confidence: 99%

A Novel Al-Bridged Trinuclear Iron(II) Bis(imino)pyridyl Complex with Catalytic Ethylene Polymerization Behavior

Long¹,

Li²,

Ma³

et al. 2011

Bulletin of the Korean Chemical Society

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A self-assembled Al-bridged diiminopyridine-based ligand (3) was synthesized and characterized by FT-IR, ESI-MS and NMR spectroscopy. Electron spectral titrations were performed to confirm the formation of a novel trinuclear bis(imino)pyridyl iron(II) complex (4) upon addition of FeCl 2 into Al-bridged ligand 3 in methanol solution. Simultaneously, a typical bis(imino)pyridine-iron(II) complex (2) was synthesized and fully characterized. The X-ray crystal study of the iron(II) complex 2 disclosed a five-coordinate, distorted squarepyramidal structure with the tridentate N^N^N ligand and chlorides. The optimal molecular structure of 4 was obtained by means of molecular mechanics, which showed that each iron atom in the complex 4 is surrounded by two chlorides, a tridentate N^N^N ligand and one oxygen atom, supporting considerations about the possibility of six-coordinate geometry from MMAO or the ethylene access. A comparison of 4 with the reference 2 revealed a remarkable decrease of the catalytic activity and MMAO consumption (activity up to 0.41 × 10 3 kg mol , Al/Fe = 1600 for 2).

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Ethylene Polymerization with a Highly Active and Long-Lifetime Macrocycle Trinuclear 2,6-Bis(imino)pyridyliron

Cited by 61 publications

References 30 publications

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

A Novel Al-Bridged Trinuclear Iron(II) Bis(imino)pyridyl Complex with Catalytic Ethylene Polymerization Behavior

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