Titanium complexes phosphorus

Alkyhdene derivatives of titanium and of phosphorus catalyse methylene exchange between olefins. Although exchange of CH2 groups is not useful for synthesis, these systems provide insight into the mechanisms of alkylidene exchange, a basic step in conventional metathesis. Titanacyclobutenes have been isolated from reactions of acetylenes with methylene-titanium complexes but titanacyclobutanes, the assumed intermediate for the case of olefins, have not been isolated. Bis(cyclopentadiene)titanacyclohexane decomposes to produce ethylene as the major product apparently via a-C-C bond cleavage. ... 

In contrast to the low yield when hydrogen chloride is employed, an 88% yield of 2,4,6-triphenyl- 1,3,5-triazine (7) is obtained when chlorosulfonic acid is used as catalyst in a molecular ratio of 3 1 (CiSOjH/PhCN) at 0-5 C C and a reaction time of 12 to 24 hours.174 Trifluo-romethanesulfonic acid as a catalyst and solvent trimerizes benzonitrile at 91 °C in a yield of 66%.175 Lewis acids alone, such as aluminum, zinc, iron or titanium chlorides, phosphorus pentachloride, and boron trifluoride, have a considerably lower catalytic activity than the corresponding mixtures of Lewis acid with various promotors, such as mineral acids, organic acids and water. These differences are attributed to a change in the structure of the active complexes with the aryl cyanides. 

It is particularly interesting, that some titanium and tantalum carbene complexes olefinate derivatives of carboxylic acids. These reagents are, moreover, much less basic than phosphorus ylides, and thus enable the olefination of strongly C-H acidic carbonyl compounds. 

Cationic mechanisms are much more characteristic of the polymerization of oxygen heterocycles, both ethers and acetals. A wide variety of catalysts has been used, including protonic acids, such Lewis acids as boron trifluoride, phosphorus pentafluoride, stannic chloride, antimony pentachloride, titanium tetrachloride, zinc chloride, and ferric chloride, and salts of carbocations or tri-alkyloxonium ions having anions derived from Lewis acids. Some complex, coordination catalysts that appear to operate by a mechanism... 

Titanacyclopropenes 31 reacts smoothly with dichlorophosphines or phosphorus trichloride with extrusion of the titanium fragment and formation of the phosphirenes 32 or 33, respectively. The transition metal complexes themselves are generated in situ from either a dichlorotitanium complex (Equation 26) or tetraisopropoxytitanium (Equation 27) by reactions with alkynes <19980M2677>. Analogous chemistry can be carried out with zircona-cyclopropenes <1998CC1177>. 

Tungsten and Nitrogen, Phosphorus, Arsenic, Antimony, and Bismuth—Complex Salts containing Vanadium—Carbides—Complex Cyanogen Derivatives— Compounds with Silicon, Titanium, 2areonium, and Boron. 

A useful alternative to phosphorus ylids are the titanium reagents, such as, 71, prepared from dicyclopentadienyltitanium dichloride and trimethylaluminum. Treatment of a carbonyl compound with the titanium cyclopentadienide complex 71 Tebbe s reagent) in toluene-THF containing a small amount of pyridine " leads to the alkene. Dimethyltitanocene (Me2TiCp2), called the Petasis reagent, is a convenient and highly useful alternative to The mechanism of Petasis... 

Halides of aluminum, silicon, and phosphorus, tin tetrachloride, titanium tetrachloride, and antimony pentachloride did not form complexes with diphenyl tellurium oxide, but converted it to the corresponding diphenyl tellurium dihalide. 

In commercial practice, all PET is made using an antimony compound for the final polycondensation stage. The transesterification reaction between DMT and the glycol is catalysed by salts of manganese, zinc, calcium, cobalt, or other metals. At the end of the ester-interchange stage, when essentially all of the methanol has been evolved, the transesterification catalyst is converted to a catalytically inactive and substantially colourless form by reaction with a phosphorus compound such as triphenyl phosphate or phosphite. Polyesters of 1,4-cyclo-hexanedimethanol and DMT or TA are made using complex titanium catalysts. 

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