Butcher, Mark Leslie (1994) A study of some novel cationic complexes of the group 4 metals and their applications in Ziegler-Natta catalysis. PhD thesis, University of Warwick.

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Abstract

The reactions between antimony(v) chloride and the monocyclopentadienyl metal trichlorides of Group 4 (CpMCl3 for M = Ti, Sr and Hf) in acetonitrile solution have afforded new hexachloroantimonate salts. These cationic metal-containing products have been isolated and characterised using IR, 1H NMR, elemental analysis, and in two cases, X-ray crystallography. The analogous pentamethylcyclopentadienyl (Cp*) systems have also been investigated, with largely similar results.

Depending on the stoichiometry employed in the reaction, the relevant mono-, di- and tri-cationic complexes can be formed via halide exchange. For the Cp/Cp*TiCl3 series, a 1:1 or 2:1 ratio of Sb:Ti affords [CpTiCl2(MeCN)3][SbCl6] and [CpTiCl(MeCN)4][SbCl6]2 respectively. A ratio of 1:6 is required to yield pure [CpTi(MeCN)5][SbCl6]3. The 16-electron, pseudo-octahedral geometry of the latter complex was confirmed by X-ray analysis.

A similar situation is found in the analogous Zr and Hf cases. However, the formation of the triply-charged complexes is accompanied by an expansion in coordination number about the metal centre; X-ray crystallographic studies revealed the 18-electron [CpZr(MeCN)6][SbCl6]3 to exhibit a pseudo-pentagonal bipyramidal geometry.

The reactivity of the CpTi3+ salt towards a variety of both neutral and anionic species has been investigated. In acetonitrile solution, the complex rects with amines to give insoluble mixtures of partially substituted products. Adduct formation with ethers and trimethylphosphine is slow and only occurs when non-coordinating solvents are employed. The complex reacts with inorganic salts to reform neutral CpTiX3 compounds by simple anion exchange.

The Ziegler-Natta catalytic activity of the cationic series has been studied. In the presence of methylaluminoxane cocatalysts, the complexes polymerise ethene but their activity is inversely proportional to the charge on the metal.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Transition metals -- Research, X-ray crystallography, Stoichiometry, Chemistry, Physical and theoretical
Official Date:	February 1994
Dates:	Date Event February 1994 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Willey, Gerald
Sponsors:	Science and Engineering Research Council (Great Britain) (SERC) ; BP International (BPI)
Format of File:	pdf
Extent:	180 leaves : ill., charts
Language:	eng
URI:	http://wrap.warwick.ac.uk/id/eprint/2542

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