Cerium bromide

CaU04 CALCIUM URANATE 474 CeBr3[g] CERIUM BROMIDE (GAS) 511... 

Figure 12.2 TG and DTG curves of complex of cerium bromide with glycine [21...

Under acidic conditions, perfluoroalkyl iodides (but not bromides) react with sodium hydrogen sulfite and cerium(IV) ions to form the corresponding sulfinates [76] (equation 69). 

An excess of a standard solution of iron(II) must therefore be added and the excess back-titrated with standard cerium(IV) sulphate solution. Erratic results are obtained, depending upon the exact experimental conditions, because of induced reactions leading to oxidation by air of iron(II) ion or to decomposition of the persulphate these induced reactions are inhibited by bromide ion in concentrations not exceeding 1M and, under these conditions, the determination may be carried out in the presence of organic matter. 

To 25.0 mL of 0.01-0.015 M persulphate solution in a 150 mL conical flask, add 7 mL of 5 M sodium bromide solution and 2 mL of 3 M sulphuric acid. Stopper the flask. Swirl the contents, then add excess of 0.05M ammonium iron(II) sulphate (15.0mL), and allow to stand for 20 minutes. Add 1 mL of 0.001 M ferroin indicator, and titrate the excess of Fe2+ ion with 0.02 M cerium(IV) sulphate in 0.5 M sulphuric acid to the first colour change from orange to yellow. 

The induced reduction of chlorate can be inhibited by iodide, bromide and chloride ions. The effectiveness of these ions is about 400 10 1 in the given order. The order and the magnitude of the effect agree fairly well with the catalytic activity of these ions in the arsenic(III)-cerium(IV) reaction. This inhibition by halides is presumably connected with the opening of a new two-electron route for the arsenic(III)-cerium(IV) reaction. 

In two-metal co-catalyst Pd-Pb-bromide catalytic packages, Pd TON also increases with lead concentration, but decreases with concentration of a second co-catalyst (Figure 2,b). However, we found that addition of a small amount of titanium or cerium is justified because it improves reaction rate and eliminates the induction period characteristic of the lead only package. As a result of optimization, the best performing catalytic packages contain about 100 molar equivalents (vs. Pd) lead, 2-4 molar equivalents of a second co-catalyst (Ti or Ce), and 600 - 800 equivalents of a quaternary bromide. 

Benzyl bromide, Molecular sieve, 2735 Benzyl chloride, Catalytic impurities, 2738 1,2-Bis(chloromethyl)benzene, 2946 Bis(2-cyanoethyl)amine, 2397 Bis(trimethylsilyl) peroxomonosulfate, 2602 Borane -tetrahydrofuran, 0138 Butylmagnesium chloride, 1641 Calcium acetylide, Methanol, 0585 Calcium chloride, 3923 Cerium, Water, 3961... 

This approach to C (1) nucleophiles has been recently extended. The Lichten-thaler zinc enolate reacts efficiently with more demanding aldehyde electrophiles to provide C-disaccharides [108,109], and activation of the C(l) bromide 276 can also be carried out using CeCl3/NaI (Scheme 72). The latter method is based on the earlier work of Ftdcuzawa [110] and others [111], although the mechanism of this cerium-mediated reaction has yet to be fully understood. 

Bromide 280 (derived by bromination of silyl enol ether 270) undergoes both zinc- and cerium-mediated cleavage under mild and essentially neutral conditions, and was used to prepare the nucleoside-containing C-glycoside 282 (Scheme 73) [ 112,113], The aldehyde 281 used in this transformation was exceptionally sensitive to basic conditions which completely precluded use of a conventional enolate obtained by deprotonation of ketone 265 (Sect. 4.3.1). 

The main processes occurring in this system are the following [219] bromate oxidizes trivalent cerium to tetravalent cerium Ce4+ oxidizes bromomalonic acid, and is reduced to Ce3+. The bromide ion, which inhibits the reaction, is isolated from the oxidation products of bromomalonic acid. During the reaction, the concentration of the Ce4+ ions (and Ce3+) oscillates several times, passing through a maximum and a minimum. The shape of the peaks of concentrations and the frequency depend on the reaction conditions. The autooscillation character of the kinetics of the cerium ions disappears if Ce4+ or Br are continuously introduced with a low rate into the reaction mixture. The autooscillation regime of the reaction takes place only in a certain interval of concentrations of the reactants [malonic... 

In this current work, cerium-modified MCM-41 mesoporous molecular sieve was synthesized using heptahydrated cerium chloride, colloidal fumed-silica, sodium hydroxide, cethyltrimethylammonium bromide and water. The incorporation of cerium to MCM-41 improved the quality, stability and acid properties of the resulting ordered mesoporous material. Its surface and structural properties were extensively studied by nitrogen adsorption and high-resolution thermogravimetry. 

The phrase laboratory curiosity was an apt characterization of a reaction that first saw the light of day in the late 1950 s1. This reaction - the acidic oxidation of citric acid by bromate in the presence of the dual catalysts bromide and cerium(IV)/(III) - displays oscillations in the concentrations of two component species in the course of proceeding towards completion. Curiosity and skepticism were engendered by oscillation in a homogeneous reaction mixture, even though such observations had been well documented in the past. 

High concentrations of catalyst (approximately 0.1 AO required for optimum reaction rates. Other metal ions, such as cerium and manganese, showed the same effect, but to a more limited extent. None of the other halogens approach bromide in activity. 

Cerium(IV) ammonium nitrate (CAN) in acetic acid oxidizes potassium bromide and, consequently, brominates methylbenzenes at a benzylic position with 50-80% yield293. f-Butyl hydroperoxide (TBHP) oxidizes CuBr2 which a-brominates toluenes to benzyl... 

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