Titanium oxide dichloride

Titanium oxide dichloride [13780-39-8] TiOCl2, is a yellow hygroscopic soHd that may be prepared by bubbling ozone or chlorine monoxide through titanium tetrachloride. It is insoluble in nonpolar solvents but forms a large number of adducts with oxygen donors, eg, ether. It decomposes to titanium tetrachloride and titanium dioxide at temperatures of ca 180°C (136). 

Titanium dibromide, 25 54 Titanium dichloride, 25 49 Titanium difluoride, 25 47 Titanium diiodide, 25 54-55 Titanium dioxide, 5 583, 25 1, 2, 15-23. See also Ti02 entries Titanium oxide entries... 

Supported oxide catalysts were discovered at the same time (8-5) as the two-component Ziegler-Natta catalysts (6, 7) in the early 1950 s. The publications on other types of one-component catalysts [supported organo-metallic compounds of transition elements (8, 9, 9a) and titanium dichloride (10) ] appeared quite recently. 

In polymerization by one-component catalysts [chromium oxide catalyst (75), titanium dichloride 159) at ethylene concentrations higher than 1 mole/liter and temperatures below 90°C the transfer with the monomer is a prevailing process. The spontaneous transfer, having a higher activation energy, plays an essential role at higher temperatures and lower concentrations of the monomer. 

Titanium white pigments, commercial production of, 19 388 Titanium white rutile pigment, 19 391 Titanium zinc oxide, 5 603 Titanium-zirconium-molybdenum (TZM) alloy, 17 14-15 Titanocene, 25 118 Titanocene catalysts, 16 19 Titanocene dichloride, 25 105 Titanocene synthons, 25 116 Titanocycles, 25 116... 

The Diels-Alder reaction outlined above is a typical example of the utilization of axially chiral allenes, accessible through 1,6-addition or other methods, to generate selectively new stereogenic centers. This transfer of chirality is also possible via in-termolecular Diels-Alder reactions of vinylallenes [57], aldol reactions of allenyl eno-lates [19f] and Ireland-Claisen rearrangements of silyl allenylketene acetals [58]. Furthermore, it has been utilized recently in the diastereoselective oxidation of titanium allenyl enolates (formed by deprotonation of /3-allenecarboxylates of type 65 and transmetalation with titanocene dichloride) with dimethyl dioxirane (DMDO) [25, 59] and in subsequent acid- or gold-catalyzed cycloisomerization reactions of a-hydroxyallenes into 2,5-dihydrofurans (cf. Chapter 15) [25, 59, 60],... 

An alternative, but related, route to allenic titanium reagents from propargylic esters has been reported recently. Reaction of titanocene dichloride with BuMgCl and Mg yields a reactive titanocene intermediate, formulated as Cp2Ti. This reduced Ti species reacts in situ by oxidative addition to propargylic acetates. The allenyltitanium reagents thus produced add to aldehydes and ketones, as expected, to afford homopropargylic alcohols (Table 9.27) [43]. 

Modified Forms in Common Use. There are numerous situations in which the foregoing system does not meet all requirements. In the formation uf binary compounds, several elements exhibit more Ilian two states of oxidation. One method, recommended by the IUPAC, of handling these situations is the use of prefixes derived from Greek to indicate stoichiometric composition, e.g., titanium dichloride, TiCL and dinitrogen oxide (nitrous oxide) N 0. Other accepted methods ofindicating proportions of constituents are the Stock system (oxidation number) and the Ewens-Bassett (charge number) system. 

Diaryl tellurium oxides were converted to diaryl tellurium dichlorides through reactions with carboxylic acid chlorides4, tin tetrachloride, titanium tetrachloride, or antimony pentachloride5. 

Oxidizer, Poison, Corrosive SAFETY PROFILE Poisonous and corrosive. Very reactive, a powerful oxidizer. Explosive or violent reaction with organic materials, water, acetone, ammonium halides, antimony, antimony trichloride oxide, arsenic, benzene, boron, bromine, carbon, carbon monoxide, carbon tetrachloride, carbon tetraiodide, chloromethane, cobalt, ether, halogens, iodine, powdered molybdenum, niobium, 2-pentanone, phosphoms, potassium hexachloroplatinate, pyridine, silicon, silicone grease, sulfur, tantalum, tin dichloride, titanium, toluene, vanadium, uranium, uranium hexafluoride. 

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