Matrix isolation and mass spectrometric studies of gas phase inorganic species
Matrix isolation and mass spectrometric studies of gas phase inorganic species
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.
University of Southampton
1992
Graham, John Terence
(1992)
Matrix isolation and mass spectrometric studies of gas phase inorganic species.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
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.
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Published date: 1992
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Local EPrints ID: 461749
URI: http://eprints.soton.ac.uk/id/eprint/461749
PURE UUID: cfddcf63-68fa-4f5b-8376-081a3f445e77
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Date deposited: 04 Jul 2022 18:53
Last modified: 04 Jul 2022 18:53
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Author:
John Terence Graham
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