10049-06-6Relevant articles and documents
Schumb, W. C.,Sundstroem, R. F.
, p. 596 - 604 (1933)
Direct epimetallation of π-bonded organic substrates with titanium(II) isopropoxide: Intermediacy of biradical, oligomeric titanium(II) reagents
Eisch, John J.,Gitua, John N.,Doetschman, David C.
, p. 1968 - 1975 (2006)
Extensive EPR experiments show that a titanium-containing molecular triplet state is formed in solution by the reaction of two equivalents of butyllithium with one equivalent of titanium(IV) isopropoxide. At higher concentrations this product, titanium(II) isopropoxide, admixed with two equivalents of lithium isopropoxide, is accompanied by the formation of a variety of nontitanium-containing side products. The powder EPR spectrum of the molecular triplet state in frozen solution is consistent with an asymmetric molecular chain of three Ti centers on which the unpaired electron centers are three metal atoms apart. Dilution experiments show that at lower concentrations, where the nontitanium-containing side products have dissipated, the intensity of the molecular triplet spectrum varies approximately linearly with concentration. Thus there is no evidence that the observed triplet molecule is one component in a series of concentration-dependent oligomerization steps. The bulky isopropoxy substituents and the coordination of the isopropoxide anions from the LiOiPr present appear to prevent closure of the Ti3 centers into an equilateral triangular diamagnetic structure. This steric hindrance, operative at the terminal diisopropoxytitanium centers and preventing closure to a ring, seems not to be observed with TiCl2·2THF, which is diamagnetic and may thus be expected to exist as an equilateral triangular cluster of three units of TiCl2·2THF, a structural model currently under further investigation. The smaller steric demand of the chloro and THF units would seem to permit octahedral coordination about each Ti center in such an equilateral trigonal array of Ti3 atoms. Chemical reactions carried out individually with diphenylacetylene, cis-stilbene or cis-stilbene oxide and titanium(II) diisopropoxide provide stoichiometric and stereochemical evidence that the attacking titanium(II) reagent is in fact the trimeric biradical. The role of the lithium isopropoxide byproduct in fostering the course of the previously reported SET reactions of titanium(II) isopropoxide and in determining the detailed structure of the open-chain Ti trimer biradical has been explicated. Wiley-VCH Verlag-GmbH & Co. KGaA, 2006.
Structural studies of the low-valent titanium "Solution": What goes on in the pinacol coupling reaction? [3]
Hashimoto,Mizuno,Matsuoka,Miyahara,Takakura,Yoshimoto,Oshima,Utimoto,Matsubara
, p. 1503 - 1504 (2001)
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Forbes, G. S.,Hall, L. P.
, p. 385 (1924)
Gaseous Species in the Ti-Al-Cl System and Reaction with H2O
Hildenbrand, D. L.,Lau, K. H.
, p. 3435 - 3437 (1991)
Chemical species in the Ti-Al-Cl system at elevated temperatures were studied by effusion-beam mass spectrometry up to 1400 K.Gaseous TiAlCl5 and TiAlCl6 were identified as products of the reaction of TiCl4(g) and a Ti-Al mixture above about 900 K, for which AlCl3, TiCl2, and TiCl3 were also present.No evidence was found for TiAlCl7.When gaseous TiCl4, AlCl3, and H2O and admitted simultaneously, TiOCl2, Al(OH)Cl2, and TiAl(OH)Cl5 were observed.All ion species showed the correct isotopic distribution.The results confirm earlier indications that AlCl3 forms gaseous complexes with divalent and trivalent Ti, but not with tetravalent Ti.
Fundamental study on synthesis and enrichment of titanium subchloride
Takeda, Osamu,Okabe, Toru H.
, p. 376 - 383 (2008)
In order to establish a new high-speed/(semi-)continuous titanium production process based on the magnesiothermic reduction of titanium subchlorides (subhalide reduction process), a novel synthetic process for obtaining titanium subchlorides (TiClx, x = 2, 3) by the reaction of titanium tetrachloride (TiCl4) with titanium metal at 1273 K was investigated. It was demonstrated that the efficiency of the TiClx formation improved drastically when molten salts were used as the reaction medium as compared with that of the synthesis by employing the direct reaction of TiCl4 gas with solid titanium. The feasibility of the enrichment process of TiClx in molten salt was also demonstrated. The method for producing the titanium subchlorides investigated in this study can be applied to the new high-speed production process of titanium.