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Title: Structural studies of halogen, interhalogen and pseudohalogen compounds of phosphorus, selenium and tellurium
Author: Khan, Rana
ISNI:       0000 0004 2707 3453
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2011
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A series of compounds with the general formula R3PX2 and R3PX4 (where R = o-tolyl, m-tolyl, p-tolyl, o-anisyl, m-anisyl, p-anisyl, o-thioanisyl, p-thioanisyl, p-fluorophenyl, p-chlorophenyl, mesityl and X = Cl, Br, I) have been synthesised and studied by X-ray crystallography, multinuclear NMR spectroscopy and Raman spectroscopy. A study of the conformational features of the aryl groups in these structures was undertaken in order to investigate the role of steric effects and crystal packing on P-X and X-X bond lengths. Compounds with the general formula RSeX / RSeX3 (where R = p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl and X = Cl, Br, I) have been synthesised by reacting the diselenides with halogens in the stoichiometric ratios. The X-ray crystal structure of p-ClC₆H₄SeI.I₂ is the first crystallographically characterised example of a compound of stoichiometry RSeI₃, although it is better represented as an I₂ adduct of a Se(II) iodide than a Se(IV) compound. In contrast, (p-FC₆H₄)Se-Se(I)₂(p-FC₆H₄) is an I₂ adduct where the Se-Se bond has not been cleaved by iodine. Both structures are stabilised by weak Se...I and I...I interactions. p-FC₆H₄SeCl₃ is an example of a dimeric structure with bridging chlorines. [Ph₄PX] and Ph₃PX₂ were reacted with PhEX (where E = Se, Te and X = I, Br, Cl) to produce salts containing [PhEX₂]- and [PhEX₄] anions. Where possible all the products were then analysed via NMR and Raman spectroscopy and X-ray crystallography. The reactions of the ligand tris-p-fluorophenyl phosphine with sulfur and selenium are presented along with the subsequent reactions of these compounds with diiodine. All of the compounds are characterised via X-ray crystallography.
Supervisor: Godfrey, Stephen Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Selenium ; Phosphorus