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Date of Award

12-17-2014

Document Type

Thesis and Dissertation-ISU Access Only

Degree Name

Master of Science (MS)

Department

Department of Chemistry

First Advisor

Lisa F. Szczepura

Abstract

This thesis is primarily concerned with the reactivity of an N-Heterocyclic carbene (NHC), N,Nâ??-bis[2,4,6-trimethylphenyl]imidazolidin-2-ylidene (SIMes), with various nitrile ligands coordinated to the hexarhenium selenide cluster core, [Re6Se8]2+. The studies described in this thesis show that SIMes exhibits reactivity other than substitution with hexarhenium selenide clusters containing p-nitrobenzonitrile, p-methoxybenzonitrile, and 2-phenylacetonitrile ligands. Specifically, SIMes was found to add to the nitrile ligands of [Re6Se8(PEt3)5(p-nitrobenzonitrile)]2+ and [Re6Se8(PEt3)5(p-methoxybenzonitrile)]2+, which contain electrophilic carbon atoms, and deprotonate the nitrile ligand of [Re6Se8(PEt3)5(Nâ?¡CCH2Ph)]2+, which contains an active methylene group. Furthermore, it has been shown that the ketimide products [Re6Se8(PEt3)5(N=C(p-nitrophenyl)(SIMes))]2+ and [Re6Se8(PEt3)5(N=C(p-methoxyphenyl)(SIMes))]2+ readily decompose in the presence of water to produce the carboxamide clusters [Re6Se8(PEt3)5(N(H)C(O)(p-nitrophenyl))]+ and [Re6Se8(PEt3)5(N(H)C(O)(p-methoxyphenyl))]+.

The coordination of benzyl isocyanide to the [Re6Se8]2+ core to produce [Re6Se8(PEt3)5(Câ?¡NCH2Ph)](SbF6)2, an organometallic hexarhenium selenide cluster, is also described. This synthesis is important for the reason that it extends the very limited organometallic chemistry of hexarhenium selenide clusters. In addition, the potential use of isocyanide ligands to produce Fischer carbenes is discussed.

Comments

Imported from ProQuest Wilson_ilstu_0092N_10408.pdf

Page Count

111

Available for download on Wednesday, May 21, 2025

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