The synthesis, structure and reactivity of organolanthanide complexes supported
by a family of novel bis(phosphinimine)carbazole and bis(phosphinimine)pyrrole pincer
ligands is presented. Through the systematic development of the ligand frameworks, rare
earth metal species with unique structure and reactivity were encountered. A variety of
complexes that exhibited unusual bonding modes were prepared and characterized by
single-crystal X-ray diffraction and multinuclear NMR spectroscopy.
Modulation of the ligand frameworks allowed for rational manipulation of the
steric and electronic environment imparted to the metal. Incorporation of a variety of
N-aryl rings (mesityl, phenyl, para-isopropylphenyl and 2-pyrimidine) and PR2 moieties
(PPh2, PO2C2H4 and PMe2) into the ligand design led to rare earth complexes that
revealed diverse reaction behaviour. In particular, C–H bond activation, sigmatropic alkyl
migration and ring opening insertion reactivity were observed. Kinetic and deuterium
labeling studies are discussed with respect to the unique reaction mechanisms
encountered during the study of these highly reactive organometallic rare earth
complexes. / xxvi, 247 leaves : ill. (some col.) ; 29 cm + 1 CD-ROM
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:ALU.w.uleth.ca/dspace#10133/3329 |
| Date | January 2012 |
| Creators | Johnson, Kevin Ross David |
| Contributors | Hayes, Paul G |
| Publisher | Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry, c2012, Arts and Science, Department of Chemistry and Biochemistry |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | en_CA |
| Detected Language | English |
| Type | Thesis |
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