Date of Award

2014

Degree Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

First Advisor

Macdonald, Charles

Keywords

Crown ether, Germanium(II), Glyme, main group, Tin(II)

Rights

CC BY-NC-ND 4.0

Abstract

Previously, crown ethers were demonstrated to be excellent ligands in the stabilization of "naked" Ge(II) dications. As an extension of this work, the reactivity of these complexes with small molecules was investigated. Herein, it is reported that the addition of one equivalent of water or ammonia to [Ge[15]crown-5][OTf]2 produces the stable complexes [Ge[15]crown-5-H2O][OTf]2 and [Ge[15]crown-5-NH3][OTf]2, respectively. The synthetic potential of these complexes is also described, investigating their deprotonated variants in pursuit of unsaturated Ge compounds, as well as their alcohol and amine analogues. The interaction of [Ge[15]crown-5][OTf]2 with heavier element hydrides was also studied. Unlike the aforementioned donor-acceptor complexes, the room temperature addition of H2S and PH3 results in the precipitation of GeS and GeP, respectively. Lastly, the suitability of glymes in the stabilization of Ge(II) and Sn(II) salts was confirmed. Both triglyme and tetraglyme complexes were isolated and structurally characterized, some with unexpected results.

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