Title

The synthesis and Characterization of Novel s-block and Lanthanide Fluoroalkoxides

Date of Award

2010

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

Karin Ruhlandt-Senge

Keywords

Lanthanides, Fluoroalkoxides

Subject Categories

Chemistry

Abstract

Examination of the new fluorinated (perfluoro- t -butoxide) and aryloxide (2-phenylphenolate) species delineates several factors responsible for their structure and function. Key elements in the coordination, aggregation behavior, and reactivity of these systems have been linked to secondary interactions, including M-Cπ, M-Nπ, M-F, and M-H(agostic) interactions. Further investigations into these often ignored interactions may provide value information into the structure-function relationships that could provide an increased understanding of the reactivity of s-block and lanthanide complexes.

This dissertation is an attempt to investigate some of the significant secondary interactions [M-F, M-Cπ and M-H(agostic)], gain insight into methods to quantify them, and determine the structure-functions relationships of the secondary interactions. Insights were provided by investigating bond-valence sums as a method to quantify the contribution toward steric saturation from secondary interactions, the role of the fluoromethyl group of the perfluoro- t -butoxide (PFTB) ligand as a donor archetype for the M-F interaction, and 2-phenylphenolate (Ompp) ligand as the prototype to further investigate the significance of M-Cπ interactions.

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