Ionic, base-free zirconocene catalysts for ethylene polymerization

Hlatky, Gregory G.; Turner, Howard W.; Eckman, R.

doi:10.1021/ja00189a064

Cited by 335 publications

(117 citation statements)

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“…This is nicely illustrated by the design of efficient Group 4 metal catalysts for olefin polymerization. Since the pioneering work of Hlatky and Turner, [10] many research groups have focussed on the design of zwitterionic titanium, zirconium, and hafnium complexes bearing a borate functionality and acting as single-component polymerization catalysts. The state-of-the-art in cyclopentadienyl-containing zwitterionic catalysts (e.g.…”

Section: Eur J Inorg Chem 2000 577ϫ591 578mentioning

confidence: 99%

Zwitterionic Organometallates

Chauvin

2000

Eur. J. Inorg. Chem.

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Section: Eur J Inorg Chem 2000 577ϫ591 578mentioning

confidence: 99%

Zwitterionic Organometallates

Chauvin

2000

Eur. J. Inorg. Chem.

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“…In particular, the small value of ∆δ(m,p-F) ϭ 3.0 ppm is consistent with the donor having displaced the anionϪcation bonding interaction; [23] an aromatic proton signal at δ ϭ 4.48 ppm strongly suggests an agostic Zr···H interaction. [26] Conclusion 1-Magnesaindane (1) was obtained via the corresponding 1-mercuraindane (6) and found to occur as a dimeric tenmembered ring species in THF solution; in line with the behavior of other magnesacycles, this is due to an interplay between ring strain and entropy. In contrast, intermediate 6 forms a dimer/trimer equilibrium, which is remarkable as, at room temperature and in the absence of a catalyst, diorganomercury compounds usually do not establish equilibria by exchanging ligands.…”

Section: 1-dicyclopentadienyl-1-zirconaindane (2)mentioning

confidence: 70%

Investigations on 1‐Metallaindanes

Goedheijt¹,

Nijbacker

Horton

et al. 2003

Eur J Inorg Chem

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1‐Mercuraindane (6) was prepared in three steps from 1‐bromo‐2‐(2‐bromoethyl)benzene (3) and converted into 1‐magnesaindane (1) by reaction with magnesium. In solution, 6 was observed to occur in a remarkable dimer/trimer equilibrium, whereas 1 forms a dimer. From 1 and dichlorozirconocene, the 1‐zirconaindane 2 was obtained, which reacted with B(C6F5)3 to form the adduct 13. According to spectroscopic data, 13 is formed by attack of the β‐methylene carbon atom at the boron atom and has a zwitterionic structure with weak interactions between the zirconium ion and one of the ortho‐fluorine atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…There are a number of general synthetic routes to Group 4 alkyl cations which have been reviewed and will be discussed below [97]. [97,108]. Using protonolysis to generate the alkyl cation leads to the generation of a Lewis base side product which can bind to the cation.…”

Section: Preparation Of Group 4 Alkyl Cationsmentioning

confidence: 99%

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

2015

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The discovery of transition metal-catalysed polymerisation of olefins in the 1950s by Ziegler and Natta was of huge importance. Over the last 30 years, the interest in homogenous polymerisation has not only grown but has changed focus from primarily studying the metallocene complexes of Group 4 to widespread exploration of postmetallocene systems. This is a consequence of extensive patenting of the metallocene catalyst systems, as well as for general interest in the improvement of polyolefin catalysis. The plastics industry produces more than 10 7 tonnes of polyethylene, polypropylene and polystyrene each year worldwide, and the study of well-defined homogenous catalysts is invaluable in uncovering the mechanism of polymerisation and the fundamental properties of the active species. This short Tutorial Review gives an overview of homogenous transition metal Ziegler-Natta catalysis in general as well as an overview of a selection of Group 4 post-metallocene catalysts. An overview of the synthesis and reactions of alkyl cations relevant to olefin polymerisation is also given. Finally, this review summarises recent advances in bimetallic catalysts for olefin polymerisation.

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Ionic, base-free zirconocene catalysts for ethylene polymerization

Cited by 335 publications

References 1 publication

Zwitterionic Organometallates

Zwitterionic Organometallates

Investigations on 1‐Metallaindanes

Group 4 metal complexes for homogeneous olefin polymerisation: a short tutorial review

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