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Neodymium Based Ziegler Catalysts – Fundamental Chemistry pp 155–281Cite as

Rare-Earth Metals and Aluminum Getting Close in Ziegler-Type Organometallics

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Part of the book series: Advances in Polymer Science ((POLYMER,volume 204))

Abstract

A prolific and synergetic interplay of rare-earth metal components and organoaluminum reagents is of fundamental importance in Ziegler-type catalysts used in diene polymerization. The present article surveys organoaluminum-promoted alkylation/cationization activation pathways which have been elaborated for various lanthanide compounds, i.e., halides, carboxylates, alkoxides, aryloxides, (silyl)amides, and hydrides. Special emphasis is put on the identification of stable discrete Ln/Al heterobimetallic complexes and the interpretation of their solution and solid-state structure (LnX n Al coordination modes). Surpassing the pure model character of many structurally evidenced Ln/Al heterobimetallics their applicability and performance in the manufacture of polydienes will be highlighted and emerging structure-reactivity relationships will be addressed. Consideration is also given to various heterogenized variants involving organopolymeric and inorganic support materials.

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Abbreviations

Ar:

aryl

Bu:

butyl

i-Bu:

isobutyl

t-Bu:

tert.butyl

CN:

coordination number

cot:

cyclooctatetraene

d:

day(s)

DIBAH:

diisobutylaluminum hydride

DME:

dimethoxyethane

DMSO:

dimethyl sulfoxide

Do:

donor

E:

heteroatom (non-carbon atom)

equiv:

equivalent(s)

Et:

ethyl

FT IR:

Fourier transform infrared spectroscopy

h:

hour(s)

Hex:

hexyl

HIBAO:

hexaisobutylalumoxane

IP:

isoprene

L:

liter(s)

Ln:

rare-earth metal (i.e., Sc, Y, La–Lu)

MAO:

methylaluminoxane

Me:

methyl

Mes:

mesityl

min:

minute(s)

MMA:

methyl methacrylate

MMAO:

modified methylaluminoxane

NMR:

nuclear magnetic resonance

Oct:

octyl

Ph:

phenyl

phen:

1,10-phenanthroline

Pr:

propyl

i-Pr:

isopropyl

py:

pyridine

rt:

room temperature

SEC:

size exclusion chromatography

TBP:

tributylphosphate

TEA:

triethylaluminum

THF:

tetrahydrofuran

TMA:

trimethylaluminum

TON:

turn over number

VT:

variable temperature

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Acknowledgments

R.A. thanks his former and current coworkers Dr. Jörg Eppinger, Dr. Michael G. Klimpel, Dr. Frank Estler, Dr. Andreas Fischbach, Dr. H. Martin Dietrich, Melanie Zimmermann, and Christian Meermann for their shared enthusiasm for Ln=Al organometallics and much fun. Our research in this field has been generously supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, DEGUSSA AG, and BAYER.AGA.F. thanks the Deutsche Forschungsgemeinschaft for a research fellowship and R.A. the Norwegian Research Council (project# 171245/V30) for financial support while writing this article.

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  1. Department of Chemistry, University of California at Berkeley, 94720, Berkeley, CA, USA

    Andreas Fischbach

  2. Department of Chemistry, Universitetet i Bergen, Allégaten 41, N-5007, Bergen, Norway

    Reiner Anwander

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Fischbach, A., Anwander, R. (2006). Rare-Earth Metals and Aluminum Getting Close in Ziegler-Type Organometallics. In: Nuyken, O. (eds) Neodymium Based Ziegler Catalysts – Fundamental Chemistry. Advances in Polymer Science, vol 204. Springer, Berlin, Heidelberg . https://doi.org/10.1007/12_093

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