Magnesium titanium trichloride

Magnesium chloride has a crystal structure very similar to violet titanium trichloride. This dictates the possibility of an epitaxial coordination of TiCU units (or TiCl3 units, after reduction) on the lateral coordinatively unsatured faces of MgCl2 crystals, giving rise to relieves crystallographically coherent with the matrix.150... 

Solutions of low-valence titanium chloride (titanium dichloride) are prepared in situ by reduction of solutions of titanium trichloride in tetrahydrofuran or 1,2-dimethoxyethane with lithium aluminum hydride [204, 205], with lithium or potassium [206], with magnesium [207, 208] or with a zinc-copper couple [209,210]. Such solutions effect hydrogenolysis of halogens [208], deoxygenation of epoxides [204] and reduction of aldehydes and ketones to alkenes [205,... 

An interesting reduction of aldehydes takes place on treatment with a reagent prepared from titanium trichloride and potassium [206] or magnesium [207] in tetrahydrofuran propionaldehyde gave a 60% yield of a mixture of 30% cis- and 30% /ronj-3-hexene [207]. 

An interesting deoxygenation of ketones takes place on treatment with low valence state titanium. Reagents prepared by treatment of titanium trichloride in tetrahydrofuran with lithium aluminum hydride [205], with potassium [206], with magnesium [207], or in dimethoxyethane with lithium [206] or zinc-copper couple [206,209] convert ketones to alkenes formed by coupling of the ketone carbon skeleton at the carbonyl carbon. Diisopropyl ketone thus gave tetraisopropylethylene (yield 37%) [206], and cyclic and aromatic ketones afforded much better yields of symmetrical or mixed coupled products [206,207,209]. The formation of the alkene may be preceded by pinacol coupling. In some cases a pinacol was actually isolated and reduced by low valence state titanium to the alkene [206] (p. 118). 

Titanium in a low valence state, as prepared by treatment of solutions of titanium trichloride with potassium [206] or magnesium [207] in tetrahydro-furan or with lithium in dimethoxyethane [206], deoxygenates ketones and effects coupling of two molecules at the carbonyl carbon to form alkenes, usually a mixture of both stereoisomers. If a mixture of acetone with other ketones is treated with titanium trichloride and lithium, the alkene formed by combination of acetone with the other ketone predominates over the symmetrical alkene produced from the other ketone [20(5] Procedure 39, p.215). 

Titanium trichloride may be prepared by reducing titanium tetrachloride with hydrogen at 600°C. The tetrachloride may alternatively be reduced with aluminum, zinc, magnesium, tin, or by electrolysis. 

TRICLORURO de TITANIO (Spanish) (7705-07-9) see titanium trichloride. TRI-CLENE or ACETYLENE TRICHLORIDE (79-01-6) C2HCI3 Forms explosive mixture with air [explosion limits in air (vol %) 12.5 to 90 flash point >200°F/>93°C autoignition temp 770°F/410°C Fire Rating 1]. Violent reaction with strong caustics (lye, potassium hydroxide, sodiiun hydroxide, etc.). Impact sensitivity results from mixtures of this material with powdered metals of aliuniniun, barium, beryllium, magnesium, and titanium. Contact with caustics, epichlorohydrin, or epoxides produces spontaneously explosive dichloroacetylene. Forms an explosive... 

Some Lewis acids such as titanium trichloride and phosphorus pentachloride Metal phosphides such as aluminum phosphide or magnesium phosphide Metal hydrides Among them, an interesting classification can be proposed regarding the nature of the products issued from the decomposition by water ... 

Catalytic activity can be considerably increased if the magnesium chloride is first combined with a suitable Lewis base, such as an ester, acid, alcohol, or amine, before reaction with an excess of titanium tetrachloride and subsequent activation with triethyl aluminum. Polyethylene produced with these catalysts has a lower molecular weight than that from the titanium trichloride catalysts mentioned earlier and less hydrogen is needed for molecular weight control. 

The magnesium supports used for polyethylene catalysts could be modified for use in polypropylene production, and magnesium chloride proved to be the most suitable when used with a Lewis base election donor. Milled magnesium chloride was known to have the same layer stracmre as a- and y-titanium trichloride with the quadrivalent titanium ion (0.068 nm diameter), being about the same size as the divalent magnesium ion (0.066 nm diameter). In 1968, Montedison and Mitsui Petrochemical Industries both disclosed the production of a highly active, very steieospecific catalyst that contained about 3% titanium on a magnesium chloride support, promoted with a Lewis base, such as ethyl benzoate. The polymer produced contained less than 1 ppm titanium with an isotactic index of more than 90%, which was improvement on the product made with previous catalysts. 

In the production of titanium, the chlorination of rutile generates approximately 0.12 tons of waste for every ton of titanium tetrachloride produced. If ilmenite is directly chlorinated, the amount of waste is 1.5 tons for every ton of titanium tetrachloride. Large amounts of ferric chloride are produced along with volatile chlorides and oxychlorides (e.g., aluminum trichloride, silicon tetrachloride, carbon oxychloride, tin tetrachloride, vanadium tetrachloride, vanadium oxychloride) these can be removed by selective distillation. In flu-idized-bed chlorination, the build-up of liquid calcium chloride and magnesium chloride in the fluid bed interferes with the process of fluidization and hence these must be removed. 

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