Titanium atoms, reactions

The 1-alkoxytitatranes can be synthesized by the reaction of equimolar amounts of tetraalkyl titanates and triethanolamine (105). X-ray crystallographic analysis of the soHd isolated from the reaction of one mole of triethanolamine and one mole of TYZOR TPT confirms the stmcture as a centrosymmetric dimer having a Ti isopropoxy nitrilotriethoxy ratio of 1 1 1. The titanium atoms have achieved a coordination number of six via a rather unsymmetrical titanium—oxygen bridge (106). 

A new process developed by Institut Francais du Petrole produces butene-1 (1-butene) by dimerizing ethylene.A homogeneous catalyst system based on a titanium complex is used. The reaction is a concerted coupling of two molecules on a titanium atom, affording a titanium (IV) cyclic compound, which then decomposes to butene-1 by an intramolecular (3-hydrogen transfer reaction. ... 

Transition-metal atoms have been shown to deoxygenate epoxides to alkenes (36). Chromium and titanium atoms emerged as the most effective species in this regard, abstracting over two equivalents of oxygen. By studying the reaction of a wide range of epoxides with chromium atoms, the reaction... 

The IR study of the reaction of titanium atom with SiH4 at 12 K in argon matrices revealed, among other products, the hydridesilyl complexes 77 and 78 with two and three agostic Ti H Si interactions, respectively. The reaction occurs... 

A number of heterogeneous systems have been developed for oxidation reactions using H2O2 as oxygen source . In 1981, Taramasso, Notari and collaborators at Enichem opened new perspectives in this field with the discovery of the Ti-silicalite (TS-1) ° , a new synthetic zeolite of the ZSM family. In the TS-1 zeolite, titanium atoms are located in vicariant positions in the place of Si atoms in the crystalline framework . The remarkable reactivity of TS-1 is likely ascribable to the site-isolation of tetrahedral Ti(IV) in a hydrophobic environment. TS-1 has proved to be an efficient catalyst for the epoxidation of unfunctionalized short-chain olefins, especially terminal ones (equation 28). In addition, polyunsaturated compounds are mainly converted into the mono epoxides (equation 29). 

The only route to dibenzenetitanium so far described is the reaction of titanium atoms with benzene the reductive routes that give access to arene complexes of Group V and VI metals fail for titanium. Although yields of about 30% are reported for the preparation of dibenzene-, ditoluene-, and dimesitylenetitanium, the reactions are more sensitive than most to the effect of excess metal. Unless the ligand-to-titanium ratio is high and the rate of deposition of titanium vapor kept low, the products seem to be catalytically decomposed by finely divided Ti metal 4a, 7). 

Historically the most commonly used lithium intercalation compound was titanium disulphide, TiS2- This compound has a layered structure of covalently bound S-Ti-S stacks held together by weak van der Waals forces. Each stack is formed by a layer of titanium atoms between two layers of sulphur atoms in a hexagon ally close packed arrangement, Lithium ions can be readily intercalated between the stacks, and if the intercalation level x is maintained below unity, the process induces only a modest and reversible expansion along the c axis (Fig. 7.13). The electrochemical reaction of the Li/TiS2 couple... 

In the process of photocatalysis, the electrons and holes produced on photoirradiated Ti02 powders are trapped at the particle surface to form unpaired-electron species (step (4) in Fig.D.3). Photocatalytic reactions are actually the reactions of these radicals with reactant molecules at the Ti02 surface. Electron spin resonance (ESR) spectroscopy has been used for the detection of the photoproduced radicals on Ti02 at low temperatures such as 77 K. It has been reported that photoproduced electrons are trapped at various different sites titanium atoms on the surface or inside the particles, or oxygen molecules adsorbed on the surface. On the other hand, photoproduced holes are trapped at lattice OAygen atoms near the particle surface or at surface hydroxyl groups. We analyzed these radical species for several Ti02 photocatalysts that are commercially available, and found that the differences in the photoproduced radicals resulted from different heat-treatment conditions and the reactivity with several molecules.17)... 

The structure of the titanium-tartrate derivatives has been determined,25,26,31 37 and based on these observations together with the reaction selectivity, a mechanistic explanation has been proposed (Scheme 9.3).38 The complex 1 contains a chiral titanium atom through the appendant tartrate ligands. The intramolecular hydrogen bond ensures that internal epoxidation is only favored at one face of the allyl alcohol. This explanation is in accord with the experimental observations that substrates with an a-substituent (b = alkyl a = alkyl or hydrogen) react much slower than when this position is not substituted (b = hydrogen). 

The melting point of titanium is 1670°C, while that of aluminium is 660°C.142 In kelvins, these are 1943 K and 933 K, respectively. Thus, the temperature 625°C (898 K) amounts to 0.46 7melting of titanium and 0.96 melting of aluminium. Hence, at this temperature the aluminium atoms may be expected to be much more mobile in the crystal lattices of the titanium aluminides than the titanium atoms. This appears to be the case even with the Ti3Al intermetallic compound. The duplex structure of the Ti3Al layer in the Ti-TiAl diffusion couple (see Fig. 5.13 in Ref. 66) provides evidence that aluminium is the main diffusant. Otherwise, its microstructure would be homogeneous. This point will be explained in more detail in the next chapter devoted to the consideration of growth kinetics of the same compound layer in various reaction couples of a multiphase binary system. 

Transition-metal-catalysed epoxidations work only on allylic alcohols, so there is one limitation to the method, but otherwise there are few restrictions on what can be epoxidized enantioselectively. When this reaction was discovered in 1981 it was by far the best asymmetric reaction known. Because of its importance, a lot of work went into discovering exactly how the reaction worked, and the scheme below shows what is believed to be the active complex, formed from two titanium atoms bridged by two tartrate ligands (shown in gold). Each titanium atom retains two of its isopropoxide ligands, and is coordinated to one of the carbonyl groups of the tartrate ligand. The reaction works best if the titanium and tartrate are left to stir for a while so that these dimers can form cleanly. 

The precipitate prepared at 80° C. at about the stoichiometric AlEta/TiCE ratio of H has a reddish-brown color, and, according to x-ray analysis, consists of 3-TiCla, whereas the product prepared at 170° C. at the same Al/Ti ratio has a purple color and the structure of 7-TiCE (4, 24, 26). Analysis further showed that the TiCE thus formed contains an appreciable amount of aluminum compounds, and if prepared at 80° C., also some ethyl groups. These aluminum compounds, which apparently consist mainly of A1CE, and possibly of some AEEtCE, are taken up in the crystal lattice of the TiCE since they could not be removed by washing and hardly show up in the x-ray diagram (4, 24). About one out of every six titanium atoms is replaced by aluminum in the 80° C. solid reaction product (4), whereas in the 170° C. product, this... 

Figure 10.9. Photochemical reactions taking place at the surface of a TiO, pigment (I) photo reduction of the titanium atom resulting in the production of hydroxyl radical (II) reduced titanium atom reacting with oxygen to form an unstable complex (III) reaction of the complex with water to produce peroxyl radicals. Both the hydroxyl and peroxyl radicals can react with the polymer matrix and initiate degradation.

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