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Date of Award
12-17-2014
Document Type
Thesis-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.
Recommended Citation
Wilson, Wade Bruce, "Synthesis, Characterization, and Reactivity of Hexarhenium Selenide Cluster Complexes Containing Carbon-Coordinating Ligands" (2014). Theses and Dissertations. 384.
https://ir.library.illinoisstate.edu/etd/384
DOI
http://doi.org/10.30707/ETD2014.Wilson.W
Page Count
111
Comments
Imported from ProQuest Wilson_ilstu_0092N_10408.pdf