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Homogeneous Catalysis Using Lanthanide Amidinates and Guanidinates

  • Frank T. EdelmannEmail author
Chapter
Part of the Structure and Bonding book series (STRUCTURE, volume 137)

Abstract

For decades, the organometallic chemistry of the rare earth elements was largely dominated by the cyclopentadienyl ligand and its ring-substituted derivatives. A hot topic in current organolanthanide chemistry is the search for alternative ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations. Among the most successful approaches in this field is the use of amidinate ligands of the general type [RC(NR )2] (R = H, alkyl, aryl; R = alkyl, cycloalkyl, aryl, SiMe3) which can be regarded as steric cyclopentadienyl equivalents. Closely related are the guanidinate anions of the general type [R2NC(NR )2] (R = alkyl, SiMe3; R = alkyl, cycloalkyl, aryl, SiMe3). Two amidinate or guanidinate ligands can coordinate to a lanthanide ion to form a metallocene-like coordination environment which allows the isolation and characterization of stable though very reactive amide, alkyl, and hydride species. Mono- and trisubstituted lanthanide amidinate and guanidinate complexes are also readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts, for example, for ring-opening polymerization reactions. This article covers the success story of lanthanide amidinates and guanidinates and their transition from mere laboratory curiosities to efficient homogeneous catalysts.

Keywords

Amidinates Guanidinates Lanthanides Organolanthanide chemistry Polymerization catalysis 

Abbreviations

AN

Acrylonitrile

CL

ε-Caprolactone

Cp

η5-Cyclopentadienyl

Cp

η5-(Trimethylsilyl)cyclopentadienyl

Cp

η5-Pentamethylcyclopentadienyl

Cy

Cyclohexyl

Dipp

2,6-Di(isopropyl)phenyl, C6H3Pr2 i–2,6

DippForm

[HC(NDipp)2]

EBI

Ethylene-bis(η5-indenyl)

Giso

[Cy2NC(NR)2] (R = C6H3Pr2 i–2,6)

HSAB

Hard and soft acids and bases

Mes

Mesityl, C6H3Me3–2,4,6

MMA

Methylmethacrylate

PHB

Poly(hydroxy-3-butyrate)

PMMA

Poly(methylmethacrylate)

ROP

Ring-opening polymerization

THF

Tetrahydrofuran

TIBAO

Isobutyl alumoxane

TMC

Trimethylene carbonate

TMEDA

N​,N​,N ​, N -tetramethylethylenediamine

TMS

Trimethylsilyl

Notes

Acknowledgements

Financial support of the author’s own work on lanthanide amidinates provided by the Deutsche Forschungsgemeinschaft (SPP1166 “Lanthanoid-spezifische Funktionalitäten in Molekül und Material”), the Fonds der Chemischen Industrie, and the Otto-von-Guericke-Universität Magdeburg is most gratefully acknowledged.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2010

Authors and Affiliations

  1. 1.Chemisches Institut der Otto-von-Guericke-Universität MagdeburgMagdeburgGermany

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