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Some aspects of the organometallic chemistry of gallium and indium
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Blacker, Nicholas Charles (1992) Some aspects of the organometallic chemistry of gallium and indium. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3251643~S15
Abstract
This thesis describes a broad study covering several aspects of the organometallic chemistry of gallium and indium.
A study has been performed on the dimethylgallium-amidine complexes formed by elimination of CH4 from mixtures of trimethylgallium and amidines. Some data have been obtained on their thermal decomposition reactions in view of their potential use as "III-V" semiconductor precursors. An X-ray crystallographic study was carried out on dimethylgallium-N,N' - diphenylbenzamidine. It was found to be monomeric, with the ligand chelating, in contrast to the only previously reported dimethylgallium derivative of a simple amidine, that of N,N * -dimethylacetamidine, which is dimeric with bridging ligands.
Two new organogallium aza-macrocycle complexes have been prepared using an unsaturated ligand 5,7,12,14-tetramethyldibenzo [b,i][ 1,4,8,11] tetraazacyclotetradecine ("H2tmtaa"). The molecular structure of both compounds has been determined by X-ray crystallography. In the dimethylgallium compound the molecule is asymmetric with the gallium atom in a tetrahedral environment co-ordinated to two nitrogen atoms on one side of the macrocydic ring. On heating, the monomethylgallium compound is produced. This provides an uncommon example of gallium in a square based pyramidal co-ordination environment, the gallium atom positioned above the centre of the N4 ring.
Work was also carried out on the co-ordination chemistry of dimethylindium iodide with ligands containing Group IS donors, particularly phosphorus, as there is a sparsity of literature covering this area. Unfortunately, no crystal structure data were obtained on compounds with phosphorus or arsenic-based ligands, but the structure of the dimethylindium iodide-TMEDA complex was determined.
Minor studies were also conducted on a potentially simple preparation of the trimethyl- and triethyl-derivatives of gallium and indium, including exchange reactions between gallium and indium trichlorides and lead tetralkyls. The stability of monomethyl and dimethyl-indium species in aqueous solution has also been investigated briefly by a quantitative N.M.R. method.
| Item Type: | Thesis or Dissertation (PhD) | ||||
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| Subjects: | Q Science > QD Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Organometallic chemistry, Gallium, Indium, Amidines | ||||
| Official Date: | 1992 | ||||
| Dates: |
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| Institution: | University of Warwick | ||||
| Theses Department: | Department of Chemistry | ||||
| Thesis Type: | PhD | ||||
| Publication Status: | Unpublished | ||||
| Supervisor(s)/Advisor: | Wallbridge, Malcolm | ||||
| Sponsors: | Science and Engineering Research Council (Great Britain) | ||||
| Extent: | xvii, 221 leaves : illustrations | ||||
| Language: | eng |
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