Victoria University

The Synthesis of Novel Gallium Carbenes, Nitrenes, Phosphinidenes and Alkoxides

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dc.contributor.advisor Fulton, Robin Cummins, Struan John Wright 2014-04-09T03:31:08Z 2014-04-09T03:31:08Z 2014 2014
dc.description.abstract In the present study, synthetic routes to formal double bonds between gallium and carbon (fig 1), nitrogen (fig 2), and phosphorus (fig 3) have been investigated. These synthetic routes utilised the monoanionic, four electron donor, β-diketiminate (BDI) ligand to provide both steric and electronic stabilisation to three coordinate gallium complexes. The known di-substituted β-diketiminatogallium complexes: [(BDI)GaMe₂] and [(BDI)Ga(NHPh)₂], as well the new complexes: [(BDI)GaBn₂], [(BDI)Ga(NHDMP)₂] (DMP = 2,6-Me₂C₆H₃), [(BDI)Ga(NHDIPP)₂] (DIPP = 2,6-iPr₂C₆H₃), [(BDI)Ga(PHPh)₂] were examined for their reactivity towards the α-proton elimination mechanism for the formation of multiple bonds that is observed in transition metals. All of these complexes were shown to be unreactive towards α-proton elimination. The di-substituted β-diketiminato-gallium complex [(BDI)GaMe₂] was subjected to various aniline derivatives to investigate if the methyl ligands exhibited the same reactivity as di-methyl transition metal complexes, where the methyl ligands could deprotonate the aniline to form a metal-imido complex. This complex was found to have no reactivity with anilines. The mono-substituted β-diketiminato-gallium complex [(BDI)Ga(NHDMP)Cl] was tested for its reactivity with ⁿBuLi to abstract the amide proton and eliminate LiCl to form a gallium imido complex. While the ¹H NMR spectrum of the reaction mixture showed that a reaction had occurred, the products could not be isolated for characterisation. Another mono-substituted β-diketiminato-gallium complex [(BDI)Ga(PHPh)Cl] was also tested for its reactivity with ⁿBuLi to abstract the phosphide proton and eliminate LiCl to form a gallium phosphinidene complex. The ¹H NMR spectrum and ³¹P NMR spectrum of the isolated complex revealed that it still contained a phosphide proton, however the gallium centre now appeared to be bonded to a former methine carbon of an isopropyl group of the BDI ligand (fig 32). This bond may have formed through metathesis between an intermediate containing a gallium-phosphorus double bond, and the C-H bond of the isopropyl group. Further mechanistic studies could confirm if an intermediate such as [fig 3] is formed, and the synthetic strategy altered to isolate it. The synthesis of β-diketiminato-gallium-alkoxide complexes was also attempted, however the products of these synthesises could not be isolated due to solubility issues, potentially due to polymerisation. en_NZ
dc.language.iso en_NZ
dc.publisher Victoria University of Wellington en_NZ
dc.subject Gallium en_NZ
dc.subject Carbenes en_NZ
dc.subject Co-ordination chemistry en_NZ
dc.title The Synthesis of Novel Gallium Carbenes, Nitrenes, Phosphinidenes and Alkoxides en_NZ
dc.type Text en_NZ
vuwschema.contributor.unit School of Chemical and Physical Sciences en_NZ
vuwschema.type.vuw Awarded Research Masters Thesis en_NZ Chemistry en_NZ Victoria University of Wellington en_NZ Master's en_NZ Master of Science en_NZ
vuwschema.subject.anzsrcfor 030204 Main Group Metal Chemistry en_NZ
vuwschema.subject.anzsrcseo 970103 Expanding Knowledge in the Chemical Sciences en_NZ

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