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Recent Progress in Late Transition Metal α-Diimine Catalysts for Olefin Polymerization

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Topics in Organometallic Chemistry

Part of the book series: Topics in Organometallic Chemistry

Abstract

This chapter reviews recent development of cationic α-diimine nickel(II) and palladium(II) complexes for olefin polymerization. The contributions of ligand structure to the catalytic polymerization properties of late metal complexes are particularly emphasized in this review. Unique among transition metal polymerization systems, these late metal complexes also catalyze the formation of branched polymers. The mechanisms of elemental reaction steps for these catalytic systems are discussed. The Pd(II) system also permits the copolymerization of ethylene and α-olefins with various polar comonomers, especially acrylates. Finally, a discussion of new research in ligand design is provided. A new class of cyclophane-based ligands has exhibited high thermal stability. The mechanism of copolymerizations is significantly altered, leading to elevated incorporations of polar monomers. An axial-donation hemilabile cyclic ligand is also discussed, the Ni(II) and Pd(II) complexes of which afford high molecular weight polyethylene despite their reduced steric bulk.

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Abbreviations

acac:

Acetylacetonato

An:

Acenaphthyl

Ar:

Aryl

COD:

1,5-Cyclooctadiene

t-Bu:

tert-Butyl

e-:

Electron

Et:

Ethyl

i-Pr:

Isopropyl

Keq:

Equilibrium constant

kins:

Monomer insertion rate constant

ktrap:

Monomer trapping rate constant

MA:

Methyl acrylate

MAO:

Methyl aluminoxane

Me:

Methyl

Mn:

Number-averaged molecular weight

Mw:

Weight-averaged molecular weight

NMR:

Nuclear magnetic resonance

PDI:

Polydispersity index

PE:

Polyethylene

Ph:

Phenyl

SHOP:

Shell high olefin process

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  1. Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, CA, 92697-2025, USA

    Zhibin Guan  & Chris S. Popeney

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  1. Zhibin Guan
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Guan , Z., Popeney , C. (2008). Recent Progress in Late Transition Metal α-Diimine Catalysts for Olefin Polymerization. In: Topics in Organometallic Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2008_7

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