Structural studies of Halogen, Interhalogen and Pseudohalogen Compounds of Phosphorus, Selenium and Tellurium

Abstract

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.

Date of Award	1 Aug 2011
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Stephen Godfrey (Supervisor)