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Titanium tetrachloride

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4", as a phonetic representation of the symbols of its molecular formula.

Properties and structure
is a dense, colourless liquid, although crude samples may be yellow or even red-brown. It is one of the rare transition metal halides that is a liquid at room temperature, vanadium tetrachloride| being another example. This property reflects the fact that molecules of weakly self-associate. Most metal chlorides are polymers, wherein the chloride atoms bridge between the metals. Its melting point is similar to that of Carbon tetrachloride|. is soluble in toluene and chlorocarbons. Certain arenes form complexes of the type . Bulkier ligands (L) give pentacoordinated adducts . ==Production==
Production
is produced by the chloride process, which involves the reduction of titanium oxide ores, typically ilmenite (), with carbon under flowing chlorine at 900 °C. Impurities are removed by distillation.{{cite encyclopedia|author1=Heinz Sibum |author2=Volker Güther |author3=Oskar Roidl |author4=Fathi Habashi |author5=Hans Uwe Wolf |author6=Carsten Siemers |title=Titanium, Titanium Alloys, and Titanium Compounds : The coproduction of Iron(III) chloride| is undesirable, which has motivated the development of alternative technologies. Instead of directly using ilmenite, "rutile slag" is used. This material, an impure form of , is derived from ilmenite by removal of iron, either using carbon reduction or extraction with sulfuric acid. Crude contains a variety of other volatile halides, including vanadyl chloride (), silicon tetrachloride (), and tin tetrachloride (), which must be separated. ==Applications==
Applications
Production of titanium metal The world's supply of titanium metal, about 250,000 tons per year, is made from . The conversion involves the reduction of the tetrachloride with magnesium metal. This procedure is known as the Kroll process: Production of titanium dioxide Around 90% of the production is used to make the pigment titanium dioxide (). The conversion involves hydrolysis of , a process that forms hydrogen chloride: : In some cases, is oxidised directly with oxygen: : Smoke screens It has been used to produce smoke screens since it produces a heavy, white smoke that has little tendency to rise. "Tickle" was the standard means of producing on-set smoke effects for motion pictures, before being phased out in the 1980s due to concerns about hydrated HCl's effects on the respiratory system. ==Chemical reactions==
Chemical reactions
Titanium tetrachloride is a versatile reagent that forms diverse derivatives including those illustrated below. Alcoholysis and related reactions A characteristic reaction of is its easy hydrolysis, signaled by the release of HCl vapors and titanium oxides and oxychlorides. Titanium tetrachloride has been used to create naval smokescreens, as the hydrochloric acid aerosol and titanium dioxide that is formed scatter light very efficiently. This smoke is corrosive, however. : Organic amines react with to give complexes containing amido (-containing) and imido (-containing) complexes. With ammonia, titanium nitride is formed. An illustrative reaction is the synthesis of tetrakis(dimethylamido)titanium , a yellow, benzene-soluble liquid: This molecule is tetrahedral, with planar nitrogen centers. : Complexes with simple ligands is a Lewis acid as implicated by its tendency to hydrolyze. With the ether THF, reacts to give yellow crystals of . With chloride salts, reacts to form sequentially , (see figure above), and . The reaction of chloride ions with depends on the counterion. and gives the pentacoordinate complex , whereas smaller gives . These reactions highlight the influence of electrostatics on the structures of compounds with highly ionic bonding. Redox Reduction of with aluminium results in one-electron reduction. The trichloride (Titanium(III) chloride|) and tetrachloride have contrasting properties: the trichloride is a colored solid, being a coordination polymer, and is paramagnetic. When the reduction is conducted in THF solution, the Ti(III) product converts to the light-blue adduct . Organometallic chemistry The organometallic chemistry of titanium typically starts from . An important reaction involves sodium cyclopentadienyl to give titanocene dichloride, . This compound and many of its derivatives are precursors to Ziegler–Natta catalysts. Tebbe's reagent, useful in organic chemistry, is an aluminium-containing derivative of titanocene that arises from the reaction of titanocene dichloride with trimethylaluminium. It is used for the "olefination" reactions. Reagent in organic synthesis finds occasional use in organic synthesis, capitalizing on its Lewis acidity, its oxophilicity, and the electron-transfer properties of its reduced titanium halides. It is used in the Lewis acid catalysed aldol addition Key to this application is the tendency of to activate aldehydes (RCHO) by formation of adducts such as . ==Toxicity and safety considerations==
Toxicity and safety considerations
Hazards posed by titanium tetrachloride generally arise from its reaction with water that releases hydrochloric acid, which is severely corrosive itself and whose vapors are also extremely irritating. is a strong Lewis acid, which exothermically forms adducts with even weak bases such as THF and water. ==References==
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