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A study of some co-ordination chemistry of the Group IVA elements
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Gordon, Douglas (1984) A study of some co-ordination chemistry of the Group IVA elements. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b1444548~S15
Abstract
Some co-ordination chemistry of the Group IVA chlorides was studied, with respect to the action of these elements as Ziegler-Natta catalysts.
Compounds of the type MgCl₂ MC1₄. nL (L = EtOAc; n = 4, M = Ti, Zr, Hf, Sn; n = 2, M = Ti; n = 6, M = Th; and L = EtOFm, THF, n = 4, M = Ti) were prepared and studied using i.r. and n.m.r. spectroscopy. Observations indicate that several species co-exist in solutions of these compounds. The mixed compound (MgCl₂)3 TiCl₄ (SnCl₄)2 12 EtOAc was also prepared.
The mixed titanium chloro-carboxylates TiClx (0₂CR) 4-x (x = 2, R = Me, CMe₃; x = 3, R = Me, CMe, Ph) were prepared and characterised. Hydrolysis reactions of these compounds in the solvents EtOAc and THF yielded compounds of the type [TiCl₂(0₂CR) L]₂0. An X-ray crystallographic study of the compounds [TiCl₂(0₂CPh) L]₂0 showed that two titanium atoms are bridged by two carboxylate groups and an oxygen atom.
Phosphine and amine complexes of the chlorides of titanium and zirconium were prepared and their reactions with reducing agents such as LiBH4 and sodium amalgam were studied in an attempt to prepare stabilized low oxidation state compounds of these elements. Hence some complexes of TiCl₄, TiCl₃, ZrCl₄ and (PhO)₂TiCl₂ with the ligands PEt₃, PBu₃, DPPE, DMPE, DBPE and TMEDA were prepared and characterised using 1H and 31P n.m.r. spectroscopy. The reactions of these compounds were generally complex and difficult to resolve.
| Item Type: | Thesis (PhD) | ||||
|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Chemistry, Inorganic, Organometallic chemistry, Chemical elements | ||||
| Official Date: | November 1984 | ||||
| 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| Publication Status: | Unpublished | ||||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: | Sussex European Research Centre, Imperial Chemical Industries PLC | ||||
| Extent: | [10], 295 leaves | ||||
| Language: | eng |
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