Nitrogen ligands have been little studied with gold(I) and almost no chemistry
has been described using anionic bridging nitrogen ligands. This dissertation concerns
the impact of the bridging ligands amidinate, ArNHC(H)NAr, on the chemistry of gold(I)
and, in particular, the effect of substituents on the molecular arrangement. The electronic
vs. steric effect of the substituents on the molecular arrangement of gold(I) amidinates
complexes is studied in detail. Tetra-, tri-, and dinuclear gold(I) amidinate complexes
are synthesized and characterized using X-ray diffraction. Spectroscopic and
electrochemical studies of the amidinate complexes are described. Catalytic studies
suggest that gold amidinates and related gold nitrogen complexes are the best catalyst
precursors for CO oxidation on TiO2 surface reported to date (87% conversion).
The dinuclear gold(I) amidinate complex with a Auâ ¦Au distance of 2.711(3) Ã
is rare. To our knowledge, there is only one other example of a symmetrical dinuclear
gold(I) nitrogen complex. Oxidative-addition reactions to the dinuclear gold(I) complex,
[Au2(2,6-Me2-form)2] are studied in detail and result in the formation of gold(II) complexes. The gold(II) amidinate complexes are the first formed with nitrogen ligands.
The complexes are stable at room temperature.
Mixed ligand tetranuclear gold(I) clusters and tetranuclear mixed Au-Ag metal
clusters of pyrazolate and amidinate ligands are synthesized and characterized using Xray
diffraction.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-1705 |
| Date | 02 June 2009 |
| Creators | Abdou, Hanan Elsayed |
| Contributors | Fackler, J. P. |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | Book, Thesis, Electronic Dissertation, text |
| Format | electronic, application/pdf, born digital |
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