Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.385123
Title: Matrix isolation and mass spectrometric studies of gas phase inorganic species
Author: Graham, John Terence
ISNI:       0000 0001 3509 8106
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 1992
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Abstract:
This thesis describes the characterisation of transition metal pentachlorides and pentabromides, group 1 iodates, caesium bromate and group 14 molybdates as matrix isolated species. A general introduction to the study of gas phase species with particular reference to high temperature chemistry is given. A more detailed introduction to the techniques of matrix isolation and mass spectrometry is also given. The analysis of matrix isolation infrared spectra and the use of isotopic substitution in order to deduce structural parameters for simple molecules is described, with reference to the MXO₃ ternary oxide. A detailed introduction is given to the study of the monomeric MX₅ gas phase species with particular reference to previous work on the pentacarbonyls and pentafluorides. From an analysis of band intensities and isotopic fine structure it is shown to be possible to identify the geometry of the monomeric MX₅ systems. Vaporisation of MCl₅ (M = P, Sb, Mo, Ta, Nb, Re) and MBr₅ (M = Nb, Ta) results in the production of matrix isolated monomeric pentahalides. The geometries of PCl₅, ReCl₅ and MoCl₅ have been solved in terms of either a D3h or C4v geometry. NbX₅ and TaX₅(X = Cl and Br) exhibit C4v geometries in nitrogen matrices, however in argon matrices a mixture of geometries is proposed. It is suggested that matrix isolated SbCl₅ exhibits a mixture of D3h and C4v structures. BPr₅ and ReBr₅ both undergo solid phase decomposition to yield the respective tribromides. OsCl₅ decomposes to yield an involatile tetrachloride. A combination of mass spectrometry and matrix isolation infrared spectroscopy is used to identify the gas phase species produced on vaporising the group 1 iodates and periodates. It has been possible to identify MIO₃ (M = Cs, Rb, K) as monomeric matrix isolated species and with the use of isotopic substitution a tridentate C3v coordination is proposed, which is consistent with the group 1 chlorates. Vaporisation of oxide mixtures and lead molybdate has enabled the identification of monomeric lead and tin molybdates as matrix isolated species. Analysis of the molybdenum isotopic fine structure and simple group theory indicates a bidentate C2v coordination for each system consistent with other published MXO₄ systems.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.385123  DOI: Not available
Keywords: Inorganic chemistry
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