Publication

Superbulky penta-aryl cyclopentadienyl ligands in lanthanide chemistry

van Velzen, N. J. C. 2017 [Groningen]: Rijksuniversiteit Groningen. 327 p.

Research output: ScientificDoctoral Thesis

Documents

  • Title and contents

    Final publisher's version, 492 KB, PDF-document

  • Chapter 1

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  • Chapter 2

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  • Chapter 3

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  • Chapter 4

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  • Chapter 5

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  • Chapter 6

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  • Chapter 7

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  • Summary

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  • Samenvatting

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  • Dankwoord

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  • Complete thesis

    Final publisher's version, 13 MB, PDF-document

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  • Propositions

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  • Nicolaas Johannes Cornelis van Velzen
CpBIG ligands are bulky organic molecules that consist of a five-membered cyclopentadienyl (Cp) ring with an aryl (six-membered ring) substituent on each carbon atom of the Cp ring. The Cp ring consists of five carbon atoms and the aryl rings contain one or more substituents to modify the properties of these ligands. A hydrogen atom can be removed from the Cp ring, which makes the CpBIG ligand negatively charged. As a result, it can coordinate with its Cp ring to a metal atom and form a CpBIG metal complex.
CpBIG metal complexes have special characteristics and are useful catalysts for industrial applications, but CpBIG lanthanide complexes have been studied rarely. In the current study, the properties, reactivity and selectivity a series of CpBIG complexes based on trivalent (3+) and divalent (2+) lanthanide metals was explored. The trivalent state is the most stable oxidation state.
Some of these trivalent complexes were exceptionally active catalysts for cyclization of amino-olefins. New and interesting reactivity between CpBIG sandwich complexes and some small molecules, including oxygen (O2)was observed. At the same time, reactivity studies of two similar divalent CpBIG samarium sandwich complexes showed exceptional stability towards various highly reactive small molecules that react instantaneous with other divalent samarium complexes with less bulky ligands. The findings described in this thesis confirm the special and interesting properties of CpBIG metal complexes.
Original languageEnglish
QualificationDoctor of Philosophy
Awarding Institution
Supervisors/Advisors
  • Harder, Sjoerd, Supervisor
  • Browne, Wesley, Assessment committee
  • Dorta, R. (Romano), Assessment committee, External person
  • Tamm, M., Assessment committee, External person
Award date13-Oct-2017
Place of Publication[Groningen]
Publisher
Print ISBNs978-94-034-0102-7
Electronic ISBNs978-94-034-0101-0
StatePublished - 2017

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