2012
DOI: 10.1021/om3002735
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Suppression of β-Hydride Chain Transfer in Nickel(II)-Catalyzed Ethylene Polymerization via Weak Fluorocarbon Ligand–Product Interactions

Abstract: The synthesis and characterization of two neutrally charged Ni­(II) ethylene polymerization catalysts, [2-tert-butyl-6-((2,6-(3,5-dimethylphenyl)­phenylimino)­methyl)­phenolato]­nickel­(II) methyl trimethylphosphine ((CH 3 )­FI-Ni) and [2-tert-butyl-6-((2,6-(3,5-bis­(trifluoromethyl)­phenyl)­phenylimino)­methyl)­phenolato]­nickel­(II) methyl trimethylphosphine ((CF 3 )­FI-Ni) are reported. In the presence of a Ni­(COD)2 cocatalyst, these catalysts produce markedly different polyethylenes: densely branched … Show more

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Cited by 132 publications
(90 citation statements)
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“…In contrast, with electron‐withdrawing trifluoromethyl groups linear polyethylene is formed under otherwise identical conditions . Note that an H–F interaction with the growing chain, which was suggested for early‐ and late‐transition‐metal catalysts, is clearly not operative …”
Section: Resultsmentioning
confidence: 93%
“…In contrast, with electron‐withdrawing trifluoromethyl groups linear polyethylene is formed under otherwise identical conditions . Note that an H–F interaction with the growing chain, which was suggested for early‐ and late‐transition‐metal catalysts, is clearly not operative …”
Section: Resultsmentioning
confidence: 93%
“…This result indicates that chain transfer to monomer is the predominant chain transfer pathway. Therefore, the propagation/chain transfer ratio is independent of the ethylene pressure 43 . Interestingly, the polymer branching density is largely independent of the ethylene pressure.…”
Section: Resultsmentioning
confidence: 96%
“…Similarly, the Grubbs-type catalyst bearing CF 3 group (Chart 1B) was also suggested to be unique in the formation of linear high molecular weight polyethylene due to an H···F interaction with the growing chain. 11 But recently, a nonfluorinated NO 2 -substituted catalyst was found to produce linear high molecular weight polyethylene, demonstrating that CF 3 -substituted catalyst is not unique. 7d Still, the possibility that the oxygen atoms in NO 2 group involve in similar weak interactions as fluorine atoms cannot be precluded.…”
Section: ■ Introductionmentioning
confidence: 99%