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Catalytic Sigma-Bond Metathesis and the Polymerization of 1,3-Dienes by Rare-Earth Metal Complexes

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50 Years of Structure and Bonding – The Anniversary Volume

Part of the book series: Structure and Bonding ((STRUCTURE,volume 172))

Abstract

This review is a selection of research highlights since 2010 in two main areas of rare-earth catalysis, but it is not meant to be an exhaustive treatment. Part 1 (Sect. 2) deals with advances in intra- and intermolecular hydroamination, hydrophosphination, and hydrosilylation. Part 2 (Sect. 3) covers progress in the polymerization of 1,3-dienes, and it is split into three main subsections: cis-1,4-selective and trans-1,4-selective polymerization, the 3,4-selective polymerization of isoprene, and copolymerization reactions of 1,3-dienes with alkenes.

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Abbreviations

Ad:

Adamantyl

Bn:

Benzyl

BOPA:

Bis(oxazolinylphenyl)amide

BTSA:

Bis(trimethylsilyl)amide

cat.:

Catalyst

Cp:

Cyclopentadienyl

Cp*:

Pentamethylcyclopentadienyl

Cy:

Cyclohexyl

dipp:

2,6-Diisopropylphenyl

dmba:

α-Deprotonated dimethylaminobenzyl

dme:

1,2-Dimethoxyethane

d p :

Pore diameter

DRIFT:

Diffuse reflectance infrared Fourier transform

ee:

Enantiomeric excess

Et:

Ethyl

iBu:

Isobutyl

iPr:

Isopropyl

Ln:

Rare-earth metal

Me:

Methyl

Me3TACD:

1,4,7-Trimethyl-1,4,7,10-tetraazacyclododecane(1−)

nBu:

n-Butyl

Ph:

Phenyl

PhMe:

Toluene

PMS:

Periodic mesoporous silica

r.t.:

Room temperature

tBu:

t-Butyl

T g :

Glass transition temperature

thf:

Tetrahydrofuran

T m :

Melting point (polymer)

TOF:

Turnover frequency

σ-BM:

Sigma-bond metathesis

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Acknowledgment

This work was supported by the DFG-funded transregional collaborative research center SFB/TRR 88 “3MET”.

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  1. Karlsruhe Institute of Technology, Karlsruhe, Baden-Württemberg, Germany

    Rory P. Kelly & Peter W. Roesky

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  1. Rory P. Kelly
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Correspondence to Peter W. Roesky .

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  1. University of Oxford, University of Oxford, Oxford, United Kingdom

    D. Michael P. Mingos

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Kelly, R.P., Roesky, P.W. (2015). Catalytic Sigma-Bond Metathesis and the Polymerization of 1,3-Dienes by Rare-Earth Metal Complexes. In: Mingos, D. (eds) 50 Years of Structure and Bonding – The Anniversary Volume. Structure and Bonding, vol 172. Springer, Cham. https://doi.org/10.1007/430_2015_193

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