Disproportionation compounds

According to Sheldon et al. (1986), two molecules of the 2,3-dihydropyrazines can form a mixture of the corresponding pyrazine and 1,2,3,4-tetrahydropyrazine by disproportionation. It was also observed by Masuda et al. (1980) that dehydrogenation of 2,3-dimethyl-5,6-dihydropyrazine generated the disproportionation compounds 2,3-dimethyl-1,2,5,6-tetrahydropyrazine and 5-ethyl-2,3-dimethylpyrazine in addition to the desired 2,3-dimethylpyrazine in a sodium ethoxide/ethanol solution. It was then deduced that the carbanion of 2,3-dimethyl-5,6-dihydropyrazine was formed with the base and then reacted with acetaldehyde, present in ethanol in small quantities, to yield the 5-substituted pyrazine. On the basis of this result the authors prepared in high yield a series of nine, 5-substituted, 2,3-dimethylpyr-azines by reaction of 2,3-dimethyl-5,6-dihydropyrazines with six aldehydes and three ketones under the same basic conditions. 

Early calculations of a similar kind indicated that the compound AlCl is unlikely to exist but at temperatures above about HOOK aluminium oxide AI2O3 and the trichloride AICI3 react to form the compound AlCl on cooling this disproportionates to give the trichloride and aluminium metal... 

Germanium forms divalent compounds with all the halogens. Germaniunil 1) chloride can be prepared by passing the vapour of germanium(IV) chloride (see below) over heated germanium. The reaction is reversible and disproportionation of germanium(II) chloride is complete at about 720 K at atmospheric pressure ... 

Liquid chlorine dioxide, ClOj, boils at 284 K to give an orange-yellow gas. A very reactive compound, it decomposes readily and violently into its constituents. It is a powerful oxidising agent which has recently found favour as a commercial oxidising agent and as a bleach for wood pulp and flour. In addition, it is used in water sterilisation where, unlike chlorine, it does not produce an unpleasant taste. It is produced when potassium chlorate(V) is treated with concentrated sulphuric acid, the reaction being essentially a disproportionation of chloric(V) acid ... 

In contrast to the + 2 state, copper(I) compounds are less frequently coloured and are diamagnetic, as expected since the 3d level is full. However, the copper(I) ion, unlike copper(II), is unstable in aqueous solution where it disproportionates into copper(II) and copper(O) (i.e. copper metal). 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

Titanium trifluoride [13470-08-17, TiF, is a blue crystalline solid that undergoes oxidation to Ti02 upon heating in air at 100°C (see Titanium compounds). In the absence of air, disproportionation occurs above 950°C to give TiF and titanium metal. TiF decomposes at 1200°C, has a density of 2.98 g/cm, and is insoluble in water but soluble in acids and alkafles. The magnetic moment is 16.2 x 10 J/T (1.75 -lB). 

In the absence of air, TEE disproportionates violently to give carbon and carbon tetrafluoride the same amount of energy is generated as in black powder explosions. This type of decomposition is initiated thermally and equipment hot spots must be avoided. The flammability limits of TEE are 14—43% it bums when mixed with air and forms explosive mixtures with air and oxygen. It can be stored in steel cylinders under controlled conditions inhibited with a suitable stabilizer. The oxygen content of the vapor phase should not exceed 10 ppm. Although TEE is nontoxic, it may be contaminated by highly toxic fluorocarbon compounds. 

The usual valence of indium is three, although monovalent and bivalent compounds of indium with oxygen, halogens, and Group 15 (VA) and 16 (VIA) elements ate well known. The lower valence compounds tend to disproportionate into the trivalent compound and indium metal the trivalent compounds ate stable. 

The Mn ion is so unstable that it scarcely exists in aqueous solution. In acidic aqueous solution, manganic compounds readily disproportionate to form Mn ions and hydrated manganese(IV) oxide, Mn02 2H20 in basic solution these compounds hydroly2e to hydrous manganese(III) oxide, MnO(OH). Sulfuric acid concentrations of about 400 450 g/L are required to stabilize the noncomplexed Mn ion in aqueous solutions. 

The alkah manganates(V) in strongly alkaline solution (45—50% at 0°C) are all blue. In water these manganate(V) compounds instantly disproportionate into manganate(VI) and Mn02. Lithium manganate(V), prepared by reaction of LiMnO and excess LiOH at 124°C, is an exception. This compound is relatively stable in 3% LiOH solution at 0°C and in absolute methyl alcohol. 

The purple permanganate ion [14333-13-2], MnOu can be obtained from lower valent manganese compounds by a wide variety of reactions, eg, from manganese metal by anodic oxidation from Mn(II) solution by oxidants such as o2one, periodate, bismuthate, and persulfate (using Ag" as catalyst), lead peroxide in acid, or chlorine in base or from MnO by disproportionation, or chemical or electrochemical oxidation. 

The ground state distribution of electrons in the aluminum atom is lT2T2 3T3/). The oxidation state of aluminum is +3, except at high temperatures where monovalent species such as AIQ, AIF, and AI2 have been spectrally identified At lower temperatures, these compounds disproportionate... 

Early studies of the condensation reaction on the monomer level did not give the full picture of this process and only in the 1980s was polycondensation of siloxanols studied by using oligomeric model compounds (76,77). These studies revealed that in the presence of strong protic acids three processes must be considered linear condensation (eq. 14), cyclization (eq. 15), and disproportionation (eq. 16). 

Chemica.1 Properties. Reviews of carbonyl sulfide chemistry are available (18,23,24). Carbonyl sulfide is a stable compound and can be stored under pressure ia steel cylinders as compressed gas ia equiUbrium with Hquid. At ca 600°C carbonyl sulfide disproportionates to carbon dioxide and carbon disulfide at ca 900°C it dissociates to carbon monoxide and sulfur. It bums with a blue flame to carbon dioxide and sulfur dioxide. Carbonyl sulfide reacts... 

Titanium Trifluoride. The trifluoride (121) is a blue crystalline soHd, density 2980 kg/m, ia which the titanium atoms are six-coordinate at the center of a slightly distorted octahedron, where the mean Ti—F distance is 197 pm. Titanium trifluoride [13470-08-1] is stable ia air at room temperature but decomposes to titanium dioxide when heated to 100°C. It is insoluble ia water, dilute acid, and alkaUes but decomposes ia hot concentrated acids. The compound sublimes under vacuum at ca 900°C but disproportionates to titanium and titanium tetrafluoride [7783-63-3] at higher temperatures. 

Toluene, an aLkylben2ene, has the chemistry typical of each example of this type of compound. However, the typical aromatic ring or alkene reactions are affected by the presence of the other group as a substituent. Except for hydrogenation and oxidation, the most important reactions involve either electrophilic substitution in the aromatic ring or free-radical substitution on the methyl group. Addition reactions to the double bonds of the ring and disproportionation of two toluene molecules to yield one molecule of benzene and one molecule of xylene also occur. 

In addition to the trialkyldihalo- and triaryldihalo antimony compounds, mixed dihalo compounds such as chi oroiodo triphenyl antimony [7289-82-9], (CgH3)2SbClI, have been reported (182). It has been shown, however, that such compounds disproportionate ia solutioa to give a mixture of startiag material plus products (183) ... 

Also formed by the direct combination of the elements is a red soHd compound, arsenic diiodide [13453-17-3] AS2I4 or ASI2, which melts at 130°C and dissolves in organic solvents. Treatment of this compound with water causes disproportionation. 

Other methods for preparing tertiary arsiaes have been employed, but they have limited usefiilness. These methods include the cleavage of quaternary arsonium compounds (68), the cyclodehydrohalogenation of haloarsines (69), the reaction of dia2onium salts with arsenic trichloride in the presence of a metal such as 2inc or iron (70), and the disproportionation of halo- or dihaloarsines (71). 

The strong conductance of the trimethyl compound may be because of a similar disproportionation. 

The existence of bismuthine was first demonstrated by using a radioactive tracer, Bi (8). Acid treatment of a magnesium plate coated with Bi resulted in the hberation of a volatile radioactive compound. In subsequent experiments, magnesium bismuthide [12048-46-3], Mg Bi, was treated with acid the yield, however, was only one part of bismuthine for every 20,000 parts of bismuth dissolved. Attempts to prepare bismuthine by reduction of bismuth trichloride with a borohydride have not been particularly successful. Experimental quantities ate best prepared by disproportionation of either methylbismuthine [66172-95-0], CH Bi, or dimethylbismuthine [14381-45-4], C2H. Bi (7) ... 

In the case of methylbismuthine, the disproportionation occurs upon keeping the compound at —45° C for several hours 389.1 mg of methylbismuthine yields 241.1 mg of BiH. ... 

Ghromium(VI) Gompounds. Virtually all Cr(VI) compounds contain a Cr—O unit. The cbromium (VT) fluoride [13843-28-2], CrF, is the only binary halide known and the sole exception. This fluoride, prepared by fluorinating Cr at high temperature and pressure, easily disproportionates... 

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