Anion disproportionation

The NMR spectrum indicates a planar aromatic structure. It has been demonstrated that the dianion is more stable than the radical anion formed by one-electron reduction, since the radical anion disproportionates to cyclooctatetraene and the dianion ... 

Reductive cleavage of l,2-di(a-naphthyl)ethane (NN) proceeds via radical anions ([NN] M" ) however, kinetic studies show that the radical anions disproportionate to dianions ... 

One consequence of LiAlH4 being very reactive, is that it is rather unselective. In order to improve its selectivity, various derivatives have been made that are less reactive. These derivatives usually have three of the hydride ions replaced by alkoxide ions, i.e. A1H(0R)3. We saw earlier that some mixed alkoxide/hydride aluminium anions disproportionate to form the tetra-alkoxide... 

This anion disproportionates in neutral aqueous solution to form the dianion [CoCO(CN)2NO]2- and Co(CO)3NO... 

Hydrogen peroxide (H Oj) is generated within the cells by two distinct processes 1) nonradical or enzymic generation and 2) radical or from superoxide anion disproportionation. 

RADICAL GENERATION FROM SUPEROXIDE ANION DISPROPORTIONATION... 

Reaction (11.4) is really a disproportionation reaction of the halate(I) anion 3XO 2X -E XO. ) Reaction (11.3) is favoured by the use of dilute alkali and low temperature, since the halate(I) anions, XO are thermally unstable and readily disproportionate (i.e. reaction (11.4)). The stability of the halate(I) anion, XO , decreases from chlorine to iodine and the iodate(I) ion disproportionates very rapidly even at room temperature. 

Iron hahdes react with haHde salts to afford anionic haHde complexes. Because kon(III) is a hard acid, the complexes that it forms are most stable with F and decrease ki both coordination number and stabiHty with heavier haHdes. No stable F complexes are known. [FeF (H20)] is the predominant kon fluoride species ki aqueous solution. The [FeF ] ion can be prepared ki fused salts. Whereas six-coordinate [FeCy is known, four-coordinate complexes are favored for chloride. Salts of tetrahedral [FeCfy] can be isolated if large cations such as tetraphenfyarsonium or tetra alkylammonium are used. [FeBrJ is known but is thermally unstable and disproportionates to kon(II) and bromine. Complex anions of kon(II) hahdes are less common. [FeCfy] has been obtained from FeCfy by reaction with alkaH metal chlorides ki the melt or with tetraethyl ammonium chloride ki deoxygenated ethanol. 

The most commonly used emulsifiers are sodium, potassium, or ammonium salts of oleic acid, stearic acid, or rosin acids, or disproportionate rosin acids, either singly or in mixture. An aLkylsulfate or aLkylarenesulfonate can also be used or be present as a stabilizer. A useful stabilizer of this class is the condensation product of formaldehyde with the sodium salt of P-naphthalenesulfonic acid. AH these primary emulsifiers and stabilizers are anionic and on adsorption they confer a negative charge to the polymer particles. Latices stabilized with cationic or nonionic surfactants have been developed for special apphcations. Despite the high concentration of emulsifiers in most synthetic latices, only a small proportion is present in the aqueous phase nearly all of it is adsorbed on the polymer particles. 

The most common catalysts in order of decreasing reactivity are haUdes of aluminum, boron, zinc, and kon (76). Alkali metals and thek alcoholates, amines, nitriles, and tetraalkylureas have been used (77—80). The largest commercial processes use a resin—catalyst system (81). Trichlorosilane refluxes in a bed of anion-exchange resin containing tertiary amino or quaternary ammonium groups. Contact time can be used to control disproportionation to dichlorosilane, monochlorosilane, or silane. 

The behavior of oligosiloxanediols in the presence of strong bases is different. The contribution to the overall process of the disproportionation reaction, involving a migration of the ultimate siloxane unit between siloxane molecules, is much greater and may even completely dominate the polycondensation reaction (80). The reactivity enhancement of the siloxane bond adjacent to the sHanolate anion can be understood in terms of n(0) (7 (SiO) conjugation. 

Copper(I) forms compounds with the anions of both strong and weak acids. Many of these compounds are stable and insoluble in water. Compounds and complexes of copper(I) are almost colorless because the inner >d orbital of the copper is completely filled. There is a very strong tendency for copper(I) to disproportionate in aqueous solutions into copper(Il) and metallic copper. 

Acetylenedimagnesium bromide, 66, 84, 137 Acyl-alkyl diradical disproportionations, 299 Acyl-alkyl diradical recombination, 296 Alkaline hydrogen peroxide, 10, 12, 20 Alkylation of formyl ketones, 93 Alkylation via enolate anions, 86 17a-Alkynyl steroids from 17-ketones, 67 2a-Al]yl-17jS-hydroxy-5a-androstan-3 -one, 9 5 Allylic acetoxylation, 242 Allylmagnesium bromide, 64 17 -Aminoandrost-5-en-3 -ol, 145 17 a-Aminomethy 1-5 a-androstane-3, 1718-diol, 387... 

In general, the activation energies for both cationic and anionic polymerization are small. For this reason, low-temperature conditions are normally used to reduce side reactions. Low temperatures also minimize chain transfer reactions. These reactions produce low-molecular weight polymers by disproportionation of the propagating polymer ... 

Values of CP measured in the presence of added PMMA (for example) will depend on how the PMMA was prepared and its molecular weight (i.e. on the concentration of unsaturated ends). PMMA formed by radical polymerization in the presence of a good H-donor transfer agent (or by anionic polymerization) would have only saturated chain ends. These PMMA chains should have a different transfer constant to those formed by normal radical polymerization where termination occurs by a mixture of combination and disproportionation. This could account for some of the variation in the values of CP for this polymer... 

The relative importance of the disproportionation process (SET between two anion radicals) depends principally on the thermodynamic constant (K). It can be easily determined more or less accurately from the potential difference existing between the first cathodic peak and the second one. (An exact calculation would be possible from the thermodynamic potentials of the two reversible transfers in the absence of proton sources and at reasonable sweep rates so as to inhibit any undesirable chemical reaction.)... 

In aprotic solvents (e.g. in DMF), the reduction does not take place by an ECE-type mechanism. In the case of diphenyl sulphoxide75 it can be shown that a fast disproportionation process occurs at the stage of the substrate anion radical ... 

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