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Title: Active O,Npy,N-Titanium(IV) Fluoride Pre-Catalysts for Ethylene Polymerization; Exploring “Fluoride Effects” on Polymer Properties and Catalytic Performance
Authors: Solan, Gregory Adam
Wright, Luka A.
Hope, Eric G.
Cross, Warren B.
Singh, Kuldip
First Published: 3-Mar-2016
Publisher: American Chemical Society
Citation: Organometallics, 2016 (Articles ASAP (As Soon As Publishable))
Abstract: Three examples of discrete six-coordinate O,Npy,N-bearing titanium(IV) trifluoride complexes, [{2-(C5H4N)-6-(CMe2O)C5H3N}TiF3] (1), [{2-(C6H4-2′-O),6-(CMe═N(2,6-i-Pr2C6H3))C5H3N}TiF3] (2a), and [{2-(3-C12H8-2-O)-6-(CMe═N(2,6-i-Pr2C6H3))C5H3N}TiF3] (3a), were prepared using a one-step HF elimination protocol from cis-[(THF)2TiF4] and the corresponding pincer ligand precursor (HL1, HL2H, and HL2Ph). A mer configuration of the three fluoride ligands is adopted in their solid-state structures, which is mirrored in solution, as shown by mutual two-bond F–F coupling in their 19F{1H} NMR spectra. For purposes of comparison, the chloride counterparts of 2a and 3a, [{2-(C6H4-2′-O),6-(CMe═N(2,6-i-Pr2C6H3)C5H3N}TiCl3] (2b) and [{2-(3-C12H8-2-O)-6-(CMe═N(2,6-i-Pr2C6H3))C5H3N}TiCl3] (3b), are also reported. On treatment with excess MAO, 1 is scarcely active in ethylene polymerization, 2a is more active, and the most sterically protected system, 3a, represents the most active nonmetallocene metal-fluoride precatalyst reported to date (340 g mmol–1 h–1 bar–1) and produces ultra-high-molecular-weight polyethylene (UHMWPE). Similar structure–activity correlations are displayed for chloride-containing 2b and 3b, but, in general, they are significantly more active than their fluoride counterparts, with 3b being the most productive of the series (990 g mmol–1 h–1 bar–1). Using fluoride rather than chloride in the precatalyst has a marked effect on not only the molecular weight but also the molecular weight distribution, with broad dispersities (Đ) being a feature of the polymers obtained from 2a and 3a, whereas those for chloride-containing 2b and 3b are appreciably narrower. Single-crystal X-ray structures are reported for 1, 2a, 2b, and 3a.
DOI Link: 10.1021/acs.organomet.5b00900
ISSN: 0276-7333
eISSN: 1520-6041
Embargo on file until: 3-Mar-2017
Version: Post-print
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © 2016, American Chemical Society. The file attached to this record is distributed under the Creative Commons “Attribution Non-Commercial No Derivatives” licence, further details of which can be found via the following link:
Description: The file associated with this record is under a 12-month embargo from publication in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.
Appears in Collections:Published Articles, Dept. of Chemistry

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