Design of Rare-Earth Organometallic Complexes Stabilized by Novel Cyclopentadienyl-Phosphazene and Modified Dialkylbenzylamine Ligand Regimes
Design der Seltenerd-Organometallkomplexe stabilisiert durch neue Cyclopentadienyl-Phosphazene und modifizierte Dialkylbenzylamin basierende Ligandsysteme
Alexander Petrov
Phosphane
Cyclopentadienylide
Complexes
Rare-earths
Chemistry + allied sciences
Chemie
Phosphazene
This Thesis is dedicated to the synthesis and investigation of the rare-earth metal complexes with two particular types of chelating monoanionic ligand systems:
• ortho-deprotonated N,N-dimethyl-benzylamines (dmba)–
• cyclopentadienyl-phosphazenes (CpPN)–
The first ligand system is presented by a series of side-chain modified (dmba)– ligands that have been used to study the influence of present or absent benzylic protons on the stability of homoleptic rare-earth metal tris-aryl complexes. Discussion of their synthesis, thermal stability and crystal structures composes Chapter II. The second and novel ligand system is presented by a series of CpPN-ligands with different substituents on P- and N-atoms and at the Cp-ring. A discussion of their syntheses, prototropic equilibria and molecular structures is presented in Chapter III. Cyclopentadienyl-phosphoranes are the intermediates in the CpPN ligand synthesis. Thus a new highly crowded cyclopentadienyl-phosphane skeleton, some mechanistic aspects of its formation, its reactivity toward oxidants and some examples of coordination chemistry of this new ligand are reported in Chapter IV. Finally, a detailed study on the synthesis and analysis of the coordination modes of the rare-earth metal CpPN-complexes with different ligands and metals is presented in Chapter V. An additional contribution to this work is the development of a simple and versatile synthesis of anhydrous etherates [LnBr3(solv)n] that are very promising precursors for the coordination and organometallic chemistry of the rare-earth metals. Combined with some general considerations on rare-earth metal chemistry this contribution is discussed in Chapter I of this Thesis.
Philipps-Universität Marburg
Marburg
Deutschhausstraße 9, 35037 Marburg
Jörg
Sundermeyer
Prof.
2008
2008-08-12
2008-10-08
2022-03-30
Text
doctoralThesis
urn:nbn:de:hebis:04-z2008-04970
eng
thesis.doctoral
Philipps-Universität Marburg
Marburg
1
https://archiv.ub.uni-marburg.de/diss/z2008/0497/pdf/darp.pdf
10.17192/z2008.0497
https://archiv.ub.uni-marburg.de/diss/z2008/0497
https://rightsstatements.org/vocab/InC-NC/1.0/