Aminopyridinato-ligand-stabilized lanthanoid complexes [Elektronische Ressource] : synthesis, reactivity, ethylene and isoprene polymerization / vorgelegt von Christian Döring

Aminopyridinato-Ligand-Stabilized Lanthanoid
Complexes: Synthesis, Reactivity, Ethylene and
Isoprene Polymerization



DISSERTATION



Zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften (Dr. rer. nat.)
im Fach Chemie der Fakultät für Biologie, Chemie und Geowissenschaften
der Universität Bayreuth






vorgelegt von
Dipl. Chem. Christian Döring
geboren in Nordhausen




Bayreuth, 2009 The following work has been carried out from Oktober 2006 to July 2009 at the Chair of
Inorganic Chemistry II of the Universität Bayreuth under the supervision of Prof. Dr. Rhett
Kempe.



This thesis fulfils the requirements of the doctoral degree of the faculty of Biology, Chemistry
and Geological Sciences at the University of Bayreuth.



Thesis submitted: 28.07.2009
Date of Scientific Colloquium: 28.10.2009








First examinator: Prof. Dr. Rhett Kempe
Second examinator: Prof. Dr. Rainer Schobert
Third examinator: Prof. Dr. Axel Müller
Chairman: Prof. Dr. Jürgen Senker








Für meine Eltern
in Dankbarkeit

















„Aller Anfang ist leicht, und die letzten Stufen werden am schwersten und seltensten
erstiegen.“
Johann Wolfgang von Goethe
Abbreviations

Å Ångström
ApH aminopyridine
Ap*H (2,6-diisopropyl-phenyl)-[6-(2,4,6-triisopropyl-phenyl)-pyridin-2-yl]-
amine
br broad
iBu iso-butyl
BuLi n-butyllithium
°C degree celsius
calcd calculated
CCTP coordinative chain transfer polymerization
Cp cyclopentadienyl
δ chemical shift (ppm)
d doublet
equiv equivalent
Et ethyl
h hours
J coupling constant (Hz)
KKTP koordinative Kettentransfer Polymerisation
Me methyl
NMR nuclear magnetic resonance
Ln rare earth metal, Sc, Y
Ph phenyl
ppm parts per million
iPr iso-propyl
py 2-pyridyl
q quartet
s singlet
sept septett
t triplet
thf tetrahydrofurane
TIBAO tetraisobutylalumoxane Table of Contents

1. Zusammenfassung / Summary .................................................................. 1
2. Introduction................................................................................................. 5
3. Overview of Thesis Results........................................................................ 9
3.1. Selective Assembly of Trinuclear Rare Earth Alkyl Hydrido Clusters
Supported by Aminopyridinato Ligands ................................................................. 9
3.2. Synthesis and Structure of Aminopyridinate-Stabilized Yttrium and
Lanthanum Amides and their Reactivity towards Alkylaluminium Compounds ... 9
3.3. Scandium Aminopyridinates: Synthesis, Structure and Isoprene
Polymerization ...................................................................................................... 10
3.4. Aminopyridinate-Stabilized Lanthanoid Complexes: Synthesis, Structure and
Polymerization of Ethylene and Isoprene ............................................................. 11
3.5. Individual Contribution to Joint Publications ....................................................... 12
4. Selective Assembly of Trinuclear Rare Earth Alkyl Hydrido
Clusters Supported by Aminopyridinato Ligands ................................ 15
4.1. Introduction ........................................................................................................... 15
4.2. Results and Disscussion ........................................................................................ 16
4.3. Conclusion............................................................................................................. 21
4.4. Acknowledgment .................................................................................................. 21
4.5. References ............................................................................................................. 21
4.6. Supporting Information ......................................................................................... 24
5. Synthesis and Structure of Aminopyridinate-Stabilized Yttrium
and Lanthanum Amides and their Reactivity towards
Alkylaluminium Compounds .................................................................. 32
5.1. Introduction ........................................................................................................... 32
5.2. Results and Discussion.......................................................................................... 33
5.3. Conclusions ........................................................................................................... 39
5.4. Experimental Section ............................................................................................ 40
5.5. Acknowledgments................................................................................................. 44
5.6. References ............................................................................................................. 44
6. Scandium Aminopyridinates: Synthesis, Structure and Isoprene
Polymerization .......................................................................................... 47 6.1. Introduction ........................................................................................................... 47
6.2. Results and Discussion.......................................................................................... 48
6.3. Conclusions ........................................................................................................... 59
6.4. Experimental Section ............................................................................................ 60
6.5. Acknowledgments................................................................................................. 66
6.6. References ............................................................................................................. 66
7. Aminopyridinate-Stabilized Lanthanoid Complexes: Synthesis,
Structure and Polymerization of Ethylene and Isoprene ..................... 70
7.1. Introduction ........................................................................................................... 70
7.2. Results and Discussion.......................................................................................... 71
7.3. Conclusion............................................................................................................. 80
7.4. Experimental Section ............................................................................................ 80
7.5. Acknowledgement................................................................................................. 84
7.6. References ............................................................................................................. 84
8. List of Publications ................................................................................... 88
9. Danksagung / Acknowledgment.............................................................. 90
10. Declaration / Erklärung ........................................................................... 94