Matrix isolation studies of some high temperature inorganic molecules
Matrix isolation studies of some high temperature inorganic molecules
Structural investigations of some high temperature inorganic molecules containing fluorine and/or oxygen, have been performed using the matrix isolation technique and vibrational spectroscopy. Monomeric uranium pentafluoride UF5 has been produced in the gas phase by novel routes. Infrared spectra of the matrix isolated molecule are reported (in the absence of other uranium containing species) and results are in agreement with published work. High resolution infrared spectra of matrix isolated molybdenum dioxidedifluoride Mo02F2 are reported and are consistent with a distorted tetrahedral molecule of C2v symmetry. Alkali metal hexafluorouranate V species vaporise above 3800 in vacuo. The potassium, rubidium and caesium salts KUF6, RbUF6 and CsUFc exhibit similar behaviour. Infrared spectra are interpreted in terms of a C2v bidentate coordination by the anion in argon, and a C3 v coordination in nitrogen matrices. The vaporisation of the sodium salt NaUF6 is accompanied by thermal decomposition to produce UFs in the gas phase. Results indicate a C2v bidentate coordination of the cation in both argon and nitrogen matrices. Tin, lead, hafnium, thorium and uranium tetrachlorides have been studied. Isotopically enriched 124SnC14, TO 'C14 and Th37C14 have been prepared. Results demonstrate the assignment of Td symmetry to SnC14, PbCl4 and HfC14. The complicated chlorine splitting pattern for ThC14 is consistent with a distorted tetrahedral molecule of C2v symmetry. Matrix site effects and the effect of vi position on the splitting pattern for a tetrahedral molecule are discussed in detail.Matrix isolated potassium perrhenate KRe04 has been studied by infrared spectroscopy, and caesium perrhenate CsRe04 by a combination of infrared and Raman spectroscopy. Isotopically substituted CsRe1°x804 has been prepared and isolated in argon matrices. The resultant infrared spectrum has been interpreted in terms of a bidentate coordination by the anion to give a molecule of C2 symmetry. No evidence for dimeric species was observed in contrast to previous work.
University of Southampton
1982
Arthers, Stephen Andrew
(1982)
Matrix isolation studies of some high temperature inorganic molecules.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Structural investigations of some high temperature inorganic molecules containing fluorine and/or oxygen, have been performed using the matrix isolation technique and vibrational spectroscopy. Monomeric uranium pentafluoride UF5 has been produced in the gas phase by novel routes. Infrared spectra of the matrix isolated molecule are reported (in the absence of other uranium containing species) and results are in agreement with published work. High resolution infrared spectra of matrix isolated molybdenum dioxidedifluoride Mo02F2 are reported and are consistent with a distorted tetrahedral molecule of C2v symmetry. Alkali metal hexafluorouranate V species vaporise above 3800 in vacuo. The potassium, rubidium and caesium salts KUF6, RbUF6 and CsUFc exhibit similar behaviour. Infrared spectra are interpreted in terms of a C2v bidentate coordination by the anion in argon, and a C3 v coordination in nitrogen matrices. The vaporisation of the sodium salt NaUF6 is accompanied by thermal decomposition to produce UFs in the gas phase. Results indicate a C2v bidentate coordination of the cation in both argon and nitrogen matrices. Tin, lead, hafnium, thorium and uranium tetrachlorides have been studied. Isotopically enriched 124SnC14, TO 'C14 and Th37C14 have been prepared. Results demonstrate the assignment of Td symmetry to SnC14, PbCl4 and HfC14. The complicated chlorine splitting pattern for ThC14 is consistent with a distorted tetrahedral molecule of C2v symmetry. Matrix site effects and the effect of vi position on the splitting pattern for a tetrahedral molecule are discussed in detail.Matrix isolated potassium perrhenate KRe04 has been studied by infrared spectroscopy, and caesium perrhenate CsRe04 by a combination of infrared and Raman spectroscopy. Isotopically substituted CsRe1°x804 has been prepared and isolated in argon matrices. The resultant infrared spectrum has been interpreted in terms of a bidentate coordination by the anion to give a molecule of C2 symmetry. No evidence for dimeric species was observed in contrast to previous work.
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Published date: 1982
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Local EPrints ID: 459765
URI: http://eprints.soton.ac.uk/id/eprint/459765
PURE UUID: ac727cf4-5b2f-48e6-8147-d3d50b0802fb
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Date deposited: 04 Jul 2022 17:18
Last modified: 04 Jul 2022 17:18
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Author:
Stephen Andrew Arthers
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