Polymerization of ethylene with new diimine complexes of late transition metals

Laine, Timo V.; Lappalainen, Kristian; Liimatta, Jonas; Aitola, Erkki; Löfgren, Barbro; Leskelä, Markku

doi:10.1002/(sici)1521-3927(19990901)20:9<487::aid-marc487>3.3.co;2-7

Cited by 25 publications

(45 citation statements)

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“…In line with the observations taken for other iminopyridyl late‐transition‐metal precatalysts such as 9‐aryliminocyclo[ b ]heptapyridyl nickel chlorides, the catalytic activity of Ni1 /MAO sharply decreases as the temperature is elevated from 20 °C to 70 °C; simultaneously the polyethylene molecular weight also decreases (entries 3, 6–11, Table and Fig. ).…”

Section: Resultssupporting

confidence: 84%

“…a Various ligand architectures have been developed to support the nickel center; these include the bidentate N^N, N^P, N^O, P^O, and tridentate N^N^N, N^N^O, N^P^N systems. Among the N,N ‐bidentate ligands, α‐diimines a, ( A , Scheme ) and various 2‐iminopyridine derivatives a, ( B , Scheme ) have been the most popular; the former can easily be synthesized from either simple diketones a, or acenaphthylene‐1,2‐dione and its analogues . a, The nickel complexes bearing these ligands turned out to be the precursors of very active catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Achieving branched polyethylene waxes by aryliminocycloocta[b]pyridylnickel precatalysts: Synthesis, characterization, and ethylene polymerization

Zhang

Wang

Flisak

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Cycloocta[b]pyridin-10-one was prepared to form the corresponding imino derivatives, which then reacted with (DME)NiBr 2 to form 10-aryliminocycloocta[b]pyridylnickel bromides (Ni1-Ni5). The new compounds were characterized by means of FT-IR spectroscopy as well as elemental analysis and the organic ligands were also analyzed by the NMR measurements. Furthermore, the molecular structure of a representative complex Ni3 was determined by the single crystal X-ray diffraction, indicating the distorted tetrahedral geometry around the nickel atom. Upon the activation with either methylaluminoxane (MAO) or diethylaluminium chloride (Et 2 AlCl), the title nickel complexes exhibited high activity in ethylene polymerization and produced polyethylene of low molecular weight (1.43-6.78 kg mol 21 ) and low dispersity (1.7-2.4), which suggests a single-site catalytic system. More importantly, the microstructure of the resultant polyethylene (especially degree of branching) and certain physical properties, such as T m values, can easily be modulated by selecting the proper substituents within the ligands and adjusting the polymerization conditions. This finding demonstrates that it is plausible to use a single catalyst for synthesizing different types of polyethylene on demand.10-Aryliminocycloocta[b]pyridylnickel bromides (Ni1-Ni5), upon activation with either MAO or Et 2 AlCl, exhibited high activity towards ethylene polymerization and produced polyethylenes with low molecular weight (1.43-6.78 kg mol 21 ) and low dispersity (1.7-2.4). made an equal contribution in this work.Additional Supporting Information may be found in the online version of this article.

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Section: Resultssupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Achieving branched polyethylene waxes by aryliminocycloocta[b]pyridylnickel precatalysts: Synthesis, characterization, and ethylene polymerization

Zhang

Wang

Flisak

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…Alternatively, bidentate ligands of the N^N, N^O, N^P, P^O chelating modes can also be developed to attain the same goal. The 2‐iminopyridylnickel complexes have recently drawn significant attention . For example, it was found that the precatalysts based on 5,6,7‐trihydroquinolin‐8‐one derivatives promoted ethylene polymerization, whilst the oligomerization was observed in the case of nickel precatalysts with the 2‐substituted (Cl/Ph/Me/ i ‐Pr) 8‐arylimino‐5,6,7‐trihydroquinolines .…”

Section: Introductionmentioning

confidence: 99%

Tailoring polymers through interplay of ligands within precatalysts: 8‐(Nitro/benzhydryl‐arylimino)‐7,7‐dimethyl‐5,6‐dihydroquinolylnickel halides in ethylene polymerization

Huang

Zeng

Flisak

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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A series of 8-(nitro/benzhydryl-substituted arylimino)-7,7-dimethyl-5,6-dihydroquinolines and the corresponding nickel halide complexes were synthesized and characterized. Molecular structures of representative nickel complexes were determined by single crystal X-ray diffraction, showing the dinuclear dimers with distorted square-pyramidal geometry around the nickel center. The binding energies determined by X-ray photoelectron spectroscopy (XPS) indicate the effective coordination between the sp 2 -nitrogen and nickel atoms as well as the influence of both the halogen ligands and the substituents within dihydroquinolines on the strength of the NiAN bond. Ethylene polymerization with the nickel precatalysts in presence of either methylaluminoxane or diethylaluminum chloride was explored in detail. For the complexes containing the nitro substituent within the organic ligand, the catalytic activity is inversely proportional to the electron density around the nickel core determined by XPS; such phenomenon is consistent with the conclusion of the computational study stating that the activity of precatalysts is correlated with the net charge on the metal center. In the polymerization process, unimodal and branched polyethylenes containing vinyl or vinylene groups were obtained. The nickel precatalysts bearing bulky benzhydryl within the organic ligand as well as bromide rather than chloride attached to the nickel atom produce polymers with relatively large amount of vinylene groups.

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“…Complexes can be isolated as mononuclear species or, depending on both the metal halides and the degree of substitution of the pyridine ring, as centrosymmetric dinuclear molecules. [8][9][10][11] By simple modifications of the iminopyridyl architecture, the polymerization and/or oligomerization activities of the metal complexes can be tuned. All these merits make this class of complexes advantageous over other types of metal catalyst, such as metallocenes or geometry constrained species [12][13][14][15] .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of some water soluble Zn(ii) complexes with (E)-N-(pyridin-2-ylmethylene)arylamines that regulate tumour cell death by interacting with DNA

et al. 2014

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The synthesis and spectroscopic properties of nine water soluble zinc(II) complexes of (E)-N-(pyridin-2-ylmethylene)arylamines (Ln) with the general formula [Zn(X)2(Ln)] (X = Cl−, Br−, I−; (1-8)) and [Zn(-N3)-(N3)(L3)]2 (9) are reported. The complexes were characterized by elemental analysis and their spectroscopic properties were studied using UV-Visible, fluorescence, IR and 1H NMR spectroscopies. The solid state structures of zinc(II) complexes 2-4 and 6-9 were established by single crystal X-ray crystallography. The majority of the structures are mononuclear with tetra-coordinate zinc centres (2-4, 6 and 7) except where L carries an additional donor atom capable of coordinating zinc (8), in which case the zinc atom has a distorted square pyramidal geometry. The centrosymmetric molecule of [Zn(-N3)(N3)(L3)]2 (9) is binuclear with the zinc atoms in a trigonal bipyramidal coordination environment. In general, the dichlorozinc derivatives 1, 3-5 and 8 exhibited moderately elevated in vitro cytotoxic potency towards the human epithelial cervical carcinoma (HeLa) cell line, with 4 as the best performer (IC50 value of 18 M). Apoptosis-inducing activity, assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, showed that the zinc complexes interacted with DNA and thereby interfered the DNA binding of several transcription factors to its promoter sites, thus inhibiting gene transcription required for the biological activity of cells. Accepted ManuscriptThis is an Accepted Manuscript, which has been through the RSC Publishing peer review process and has been accepted for publication.Accepted Manuscripts are published online shortly after acceptance, which is prior to technical editing, formatting and proof reading. This free service from RSC Publishing allows authors to make their results available to the community, in citable form, before publication of the edited article. This Accepted Manuscript will be replaced by the edited and formatted Advance Article as soon as this is available.To cite this manuscript please use its permanent Digital Object Identifier (DOI®), which is identical for all formats of publication.More information about Accepted Manuscripts can be found in the Information for Authors.Please note that technical editing may introduce minor changes to the text and/or graphics contained in the manuscript submitted by the author(s) which may alter content, and that the standard Terms & Conditions and the ethical guidelines that apply to the journal are still applicable. In no event shall the RSC be held responsible for any errors or omissions in these Accepted Manuscript manuscripts or any consequences arising from the use of any information contained in them. www.rsc.org/dalton ISSN 1477-9226 Dalton TransactionsAn international journal of inorganic chemistry 1477-9226(2010)

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Polymerization of ethylene with new diimine complexes of late transition metals

Cited by 25 publications

References 0 publications

Achieving branched polyethylene waxes by aryliminocycloocta[b]pyridylnickel precatalysts: Synthesis, characterization, and ethylene polymerization

Achieving branched polyethylene waxes by aryliminocycloocta[b]pyridylnickel precatalysts: Synthesis, characterization, and ethylene polymerization

Tailoring polymers through interplay of ligands within precatalysts: 8‐(Nitro/benzhydryl‐arylimino)‐7,7‐dimethyl‐5,6‐dihydroquinolylnickel halides in ethylene polymerization

Synthesis and characterization of some water soluble Zn(ii) complexes with (E)-N-(pyridin-2-ylmethylene)arylamines that regulate tumour cell death by interacting with DNA

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