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Title: Raising the N-aryl fluoride content in unsymmetrical diaryliminoacenaphthylenes as a route to highly active nickel(ii) catalysts in ethylene polymerization.
Authors: Wang, X.
Fan, L.
Yuan, Y.
Du, S.
Sun, Y.
Solan, Gregory A.
Guo, C. Y.
Sun, W. H.
First Published: 20-Oct-2016
Publisher: Royal Society of Chemistry
Citation: Dalton Transactions, 2016
Abstract: Five examples of selectively fluorinated unsymmetrical diiminoacenaphthylenes, 1-[2,6-{(4-FC6H4)2CH}2-4-FC6H4N]-2-(ArN) C2C10H6 (Ar = 2,6-Me2C6H3L1, 2,6-Et2C6H3L2, 2,6-iPr2C6H3L3, 2,4,6-Me3C6H2L4, 2,6-Et2-4-MeC6H2L5), have been synthesized and used to prepare their corresponding nickel(ii) halide complexes, LNiBr2 (Ni1-Ni5) and LNiCl2 (Ni6-Ni10). Both (1)H and (19)F NMR spectroscopy techniques have been employed to characterize paramagnetic Ni1-Ni10; an inequivalent fluorine environment is a feature of the tetrahedral complexes in solution. Upon activation with relatively low ratios (ca. 600 equiv.) of ethylaluminum sesquichloride (Et3Al2Cl2, EASC), all the nickel complexes displayed high activities toward ethylene polymerization at 30 °C with precatalyst Ni4 the standout performer at 2.20 × 10(7) g of PE per mol of Ni per h, producing highly branched polyethylenes. In comparison with related diiminoacenaphthylene-nickel catalysts, these current systems, incorporating a high fluorine content on one N-aryl group, display superior productivity. In addition, the molecular structures of Ni2 and Ni4 are reported and the active catalyst is probed using (19)F NMR spectroscopy.
DOI Link: 10.1039/c6dt03817d
ISSN: 1477-9226
eISSN: 1477-9234
Version: Post-print
Status: Peer-reviewed
Type: Journal Article
Rights: Creative Commons “Attribution Non-Commercial No Derivatives” licence CC BY-NC-ND, further details of which can be found via the following link: Archived with reference to SHERPA/RoMEO and publisher website.
Description: Electronic Supplementary Information (ESI) available: NMR spectra for the ligands L1 – L5 and complexes Ni1 – Ni10; crystallographic data in CIF format. CCDC 1504611 (Ni2) 1504612 (Ni4). Author confirms PDF is post-print.
Appears in Collections:Published Articles, Dept. of Chemistry

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