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Goffer, Zvi (1965) The reactions of aromatic hydroxy compounds with titanium(IV) halides. Doctoral thesis, Northern Polytechnic.
Reactions of phenols with titanium tetrachloride and of 8-quinolinol with covalent metal halides have been studied. Aryl titanates have been shown to be monomeric, in contrast to the alkyl titanates, which are polymeric. A preliminary investigation of the ultraviolet and visible spectra of these compounds has been made.
Reactions of the type MCl₄ + nOxH = MCl₄·nOxH (where M = Ti and Sn, OxH = 8-quinolinol, and n = 1 to 6) were studied.
When n = 1 and n = 2, adducts containing the neutral ligand 8-quinolinol are formed. The adducts were studied using thermogravimetric and differential thermal analysis, as well as infrared and visible spectroscopy. It was shown that the thermal decomposition of these compounds proceeds in the following manner:
• When n = 1: 2(MCl₄·OxH) = 2HCl + MCl₄ + MCl₂Ox₂
• When n = 2: MCl₄·2OxH = 2HCl + MCl₂Ox₂
Addition compounds of 8-quinolinol with other covalent halides were also studied; the compounds FeCl₃·2OxH and SbCl₅·OxH were prepared. Boron trichloride, however, reacted with 8-quinolinol to give BCl₂Ox.
The chemistry of 8-quinolinolates containing a molecule of 8-quinolinol is surveyed. A review on the nature of the hydrogen bond in 8-quinolinol is also included.
When n = 3 and n = 4, the products obtained are mixtures; TiCl₄·4OxH, for example, is TiCl₂Ox₂·2OxH₂Cl. Titanium tetrabromide, germanium tetrachloride, and tin tetrachloride give rise to similar mixtures. The properties of these mixtures and their components were investigated by spectroscopy, thermal techniques, mass spectrometry, and X-ray powder photography.
If n = 6, titanium tetrachloride affords TiClOx₃. TiClOx₃ and TiCl₂Ox₂ react with titanium tetrachloride:
2TiClOx₃ + TiCl₄ = 3TiCl₂Ox₂
TiCl₂Ox₂ + TiCl₄ = 2TiCl₃Ox
TiCl₂Ox₂ also reacts with hydrogen chloride to give the adduct TiCl₄·2OxH. Relevant reaction sequences are discussed.
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