Title

Placing heavy alkaline earth metals on the map: Synthetic access, structure evaluation and reactivity studies of heavy alkaline earth organometallics

Date of Award

2007

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Keywords

Alkaline earth organometallics, Alkaline eath metal acetylides, Alkaline earth metals, Di- and triphenylmethanides, Alkaline earth metal tetraphenylborates, Alkaline earth metal aryloxide

Subject Categories

Chemistry | Organic Chemistry | Physical Sciences and Mathematics

Abstract

The recent surge in the interest in heavy alkaline earth metal organometallics can be attributed to its increasing list of applications in synthetic organic, organometallic and materials chemistry. Progress in this chemistry has been thwarted by the high reactivity of the target compounds; as such further growth in this area of chemistry depends on the development of synthetic methods and detailed structure function analysis. To bridge this gap, this thesis examines synthetic methodologies and strives to increase the number of well characterized alkaline earth organometallic compounds to provide the basis for further development.

A significant portion of this work illustrates structural principles of the organometallic compounds of heavy group 2 metals and their tendency to display unexpected bent X ligand - M - X ligand geometries as demonstrated by the alkaline earth acetylides. Other aspects illuminated here pertain to the three ion association modes of the target compounds, specifically heavy alkaline earth di- and triphenylmethanides in solution and the solid state, which for the closely related organolithium compounds have been shown to affect the reactivity of the compounds.

Synthetic investigations associated with the structural examination strengthen the viability of toluene elimination and transmetallation pathways towards the entry to these species.

Accordingly, the results presented here extend the understanding of the structural models for heavy group 2 organometallic compounds while providing synthetic tools for the further development of this rapidly developing area of organometallic chemistry.

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