Metal perchlorates reactions with

Most of the complexes were conveniently prepared by the reaction in ethanol of the appropriate ligand with hydrated nickel perchlorate which had sometimes been dehydrated previously by stirring it with an excess of 2,2-dimethoxypropane or triethyl orthoformate. It must be remembered that transition metal perchlorate complexes with amines are potentially hazardous and can explode even under mild conditions. Safety precautions must be used in preparations Ni(C104)2(H20)2 has been prepared by carefully heating the hexahydrate under vacuum at about 100 °C.1584... 

Although not shown in Table 6.12, aryl metallation by reaction with mercury(II) (Equation 6.100) and thallium(III) (Equation 6.101) salts is also known. The mer-curation is commonly effected with the perchlorate [Hg(C104)2] to give the corresponding mercurial salt. Interestingly, unlike other electrophilic substitution reactions discussed above, a deuterium isotope effect indicative of rate-determining... 

A more recent synthesis of 3-methylenecephams from cephalosporins utilizes mercury salts in a metal-assisted reaction with 3-methyl-3-hal-ocepham ester sulfoxides. Although ordinarily dehydrohalogenations of 3-halo-3-methylcephams lead to the thermodynamically more stable 3-methyl-2-cephems and -3-cephems, chemists at Dista Products Limited (England) discovered that electrophilic mercury salts specifically led to 3-methylenecephams (Corfield and Taylor, 1978). When p-nitrobenzyl 7-phenoxyacetamido-3-methyl-3-bromo(or 3-iodo)cepham-4-carboxylate 1-oxide (47) was treated with mercury(I or II) perchlorate in dimethox-yethane for 18 hr at room temperature, p-nitrobenzyl 7-phenoxyacetam-ido-3-methylenecepham-4-carboxylate 1-oxide (48) was obtained in 75% yield. No other metal salt (in a variety of solvents) effected this transformation. Their view of the mechanism of this reaction is detailed later in this chapter. 

Ce4+ is a versatile one-electron oxidizing agent (E° = - 1.71 eV in HC10466 capable of oxidizing sulfoxides. Rao and coworkers66 have described the oxidation of dimethyl sulfoxide to dimethyl sulfone by Ce4+ cation in perchloric acid and proposed a SET mechanism. In the first step DMSO rapidly replaces a molecule of water in the coordination sphere of the metal (Ce v has a coordination number of 8). An intramolecular electron transfer leads to the production of a cation which is subsequently converted into sulfone by reaction with water. The formation of radicals was confirmed by polymerization of acrylonitrile added to the medium. We have written a plausible mechanism for the process (Scheme 8), but there is no compelling experimental data concerning the inner versus outer sphere character of the reaction between HzO and the radical cation of DMSO. 

Mixtures of the sulfoxide with metal salts of oxoacids are powerful explosives. Examples are aluminium perchlorate, sodium perchlorate and iron(III) nitrate [1], The water in hydrated oxosalts (aluminium perchlorate, iron(III) perchlorate, iron(III) nitrate) may be partially or totally replaced by dimethyl (or other) sulfoxide to give solvated salts useful as explosives [2], Metal nitrates and perchlorates solvated with DMSO are generally powerfully explosive, and under certain conditions a violent reaction is easily triggered [3], Several other explosions involving perchlorates and the sulfoxide have been reported. 

Alkali-immobile dye-releasing quinone compounds, 19 293-294 Alkali lignins, 15 19-20 Alkali manganate(VI) salts, 15 596 Alkali manganates(V), 15 592 Alkali-metal alkoxide catalysts, 10 491 Alkali-metal alkoxides, effects of, 14 252 Alkali-metal alkylstannonates, 24 824 Alkali-metal fluoroxenates, 17 329-330 Alkali-metal hydrides, 13 608 Alkali-metal hydroxides, carbonyl sulfide reaction with, 23 622 Alkali-metal metatungstates, 25 383 Alkali-metal perchlorates, 18 211 Alkali-metal peroxides, 16 393... 

The reaction of aminoguanidine bicarbonate (84) with sodium nitrite in the presence of excess acetic acid produces 1,3-ditetrazolyltriazine (89), another nitrogen-rich heterocycle (C2H3N11 = 85 % N) which readily forms explosive metal salts. The reaction of aminoguanidine bicarbonate (84) with sodium nitrite in the presence of mineral acid yields guanyl azide (90), of which, the perchlorate and picrate salts are primary explosives. Guanyl azide (90) reacts with sodium hydroxide to form sodium azide, whereas reaction with weak base or acid forms 5-aminotetrazole. ... 

Both the radical ion (40) and the alkali metal salts (41) react unusually with trityl perchlorate, giving 2,2, 5,5 -tetraphenyl-l,l -diarsolyl (44) as a deep red crystalline solid (m.p. 209-212 °C). This reforms the lithium or potassium salt (41) on reaction with the metal in an inert solvent (74TL303). These reactions are shown in Scheme 9. 

Bis(l,2-diaminoethane)copper(II) perchlorate undergoes reaction with acetone to give the quinquedentate complex (43), which is converted to the macrocyclic complex (44) on addition of base, usually excess 1,2-diaminoethane (Scheme 8).86 Similar cobalt(I3) complexes cannot be prepared by metal template methods. 

Perchloryl fluoride, C103 F, has been prepared by the action of elemental fluorine on potassium perchlorate,1 by the electrolysis of sodium perchlorate in anhydrous hydrogen fluoride,2 and by reactions of various metal perchlorates with fluorosulfuric acid3 or antimony(V) fluoride.4 Although the latest methods (with HS03 F or SbFs or both) are more convenient than the first ones, they suffer the disadvantages that elevated temperatures are... 

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