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Title: Halide transfer reactions of arsenic, antimony and bismuth
Author: Collins, Helen
ISNI:       0000 0000 6664 7385
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 1991
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The study of Group 15 (As, Sb, Bi) halide exchange reactions. The Lewis acidity of SbCls was displayed using various metal halides. Treatment of the metal halides MCln (n=2, M=Mg, Sn; n=3, M=Sc, Y, La, Ti, In; n=4, M=Ti, Sn) with SbCls in MeCN provided antimonate(V) salts of the type [MCln-lL7-n][SbCl6] characterised by ^lgb nmr, electronic and infra-red spectroscopy and accompanying microanalytical data. Depending upon the stoichiometry of the reactants used the antimonate salts have been formulated as [MCln-xL6-(n-x)]x+[SbCl6]x‘ (where n=2, 3, 4; x=l, 2, 3). The formation of mono-, di- and tricationic metal species has been effected by single and multiple halide abstraction, the resultant formation of 1:1. 1:2 and 1:3 electrolytes in MeCN has been confirmed by conductivity studies. The Lewis acidity and basicity of BiCl3 was illustrated by treatment of MCln (n=2, M=Mg; n=5, M=Sb respectively) with BiCl3 in MeCN. Reaction with n=2, M=Mg gave bismuthate(III) salts of the type [Mg(MeCN)6)mlBi4Cli2+2m]2m'- "1=2, 3, depending upon the stoichiometry of the reactants used. The crystal structure of the product m=2 in MeCN resulted in the hexa-coordinated magnesium [Mg(MeCN)$J2+ dication and the novel tetranuclear bismuth(III) chloro anion [Bi4Cll6l4". which contains three different types of chlorine atoms; ten terminal, four an(j two Where m=3 gave a tetranuclear anion [18- Further variation of the stoichiometry of the MgCl2/BiCl3 system did not give any other products. Conductivity measurements confirm the products as 2:1 and 3:1 electrolytes in DMF. However reaction of BiCl3 with n=3, m=Ti, V, Cr, Fe; n=4, M=Ti, Sn led to the neutral [MCI3L3] and [MCI4L2] adducts. The limited Lewis acidity of SbCl3 towards MCln was displayed by reaction of MCln (n=3, M=Ti, Fc, In, Bi; n=4, M=Ti, Sn) with SbCl3 in MeCN which gave the neutral MCInLx (L=MeCN, x=2, 3) adducts. Reaction with n=5, M=Sb provided SbCl3-SbCl5.4MeCN. The oxidation of As(III) to As(V) using chlorine and reaction with MCln (n=4, M=Ti, Sn, n=2, M=Zn) gave the MClnLx adducts. Reaction with n=2, M=Mg and MC4NCI gave [Mg(MeCN)6][AsCl6] and [Me4Nl[AsCl6l- [TiCl3(MeCN)3HSbCl6) and [TiCl2(MeCN)4][SbCl6)2 have been shown to behave as reactive centres for ligand and/or chloride exchange reactions with neutral, L' and anionic, L" ligands (L'=PPh3; L"=C1‘, Br*). Reaction with L’=PPh3 gave [TiCl3(PPh3)][SbCl6l and with L'=C|- gave TiCl4L2- Reaction of T1CI4 with MgCl2 in MeCN gave the ternary complex MgCl2.TiCl4.6MeCN.
Supervisor: Not available Sponsor: Science and Engineering Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry