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Date of Award
Thesis and Dissertation-ISU Access Only
Master of Science (MS)
Department of Chemistry
Lisa F. Szczepura
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.
Wilson, Wade Bruce, "Synthesis, Characterization, and Reactivity of Hexarhenium Selenide Cluster Complexes Containing Carbon-Coordinating Ligands" (2014). Theses and Dissertations. 384.