An investigation of novel reactivity and bonding in rare earth metal complexes
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Date
2012
Authors
Johnson, Kevin Ross David
Journal Title
Journal ISSN
Volume Title
Publisher
Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry, c2012
Abstract
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.
Description
xxvi, 247 leaves : ill. (some col.) ; 29 cm + 1 CD-ROM
Keywords
Rare earth metals , Organorare earth metal compounds