A matrix isolation study of transition metal halides and their structure.

Wilson, Antony V.

Abstract

The work within this thesis has concentrated on the formation and isolation of titanium, vanadium, palladium, and mercury halides, with emphasis on the fluorides.TiF, TiF2, TiF3, and TiF4 have all been isolated within an argon matrix and infrared spectra obtained. From the titanium isotope splitting pattern a bond angle has been determined for TiF2 for the first time of 165o, or effectively linear. This work is also the first time that TiF has been isolated within an argon matrix. Work has also been conducted with vanadium which has lead to the isolation of VF5, VF4, VF3, and VF2, with VF4 undergoing Fermi Resonance. This is the first time that VF4 and VF2, consistent with a linear structure, have been isolated within a matrix.Work conducted upon palladium led to the isolation of numerous palladium fluorides, identified by the palladium isotope patterns in their IR spectra. Due to the similarity of the calculated stretching frequencies of PdF2, PdF3, PdF4, and PdF6 the assignment was challenging and so identification of these bands was conducted based photolysis and annealing behaviour in conjunction with computational calculations. This has allowed for the assignment of the bands present to PdF6, PdF4, PdF3, PdF2, and PdF.The bond length of molecular HgF2 has also been determined for the first time at 1.94(2) Å using the Hg L3-edge with EXAFS. Although the initial aim of this work was to isolate HgF4, using IR, UV/Vis, and XANES, no evidence could be found for oxidation states of mercury higher that HgII. The work also developed a new clean way of making HgF2 in a matrix. The identification of a new Hg…X2 complex was also discovered which when photolysed forms the HgX2 compound, this has only been proven for HgF2. This was achieved by isolating mercury atoms in an argon matrix doped matrices, photolysis of this matrix the led to the formation of HgF2 in significant amounts.

Citation

Wilson, A. V. A matrix isolation study of transition metal halides and their structure. (Thesis). University of Hull. https://hull-repository.worktribe.com/output/4209348

• Thesis Type: Thesis
• Deposit Date: Aug 15, 2011
• Publicly Available Date: Feb 22, 2023
• Keywords: Physical sciences; Chemistry
• Public URL: https://hull-repository.worktribe.com/output/4209348
• Additional Information: Physical Sciences, The University of Hull
• Award Date: Jun 1, 2009