Perchlorate-Free Complexes

5-diaminotetrazole then reacts with the appropriate perchlorate to yield the final product [48]. 

Bichay and Hirlinger have recently reported the ferrous and cupric perchlorate complexes as the most promising candidates for LA replacement [48, 50]. The ferrous complex has been tested as a primary explosive in stab detonators (M59) [50]. 

A relatively new group of initiating explosives has recently been described by Americans. It is reported as a group of previously undescribed green primary explosives based on complex metal dianions and environmentally benign cations. 

The explosive performance is controlled by changing the number of the nitrotetzrazole ligands and the sensitivity by selection of the cation. Four anions with iron as the central atom denominated Fe [NT3], Fe [NT4], Fe [NT5] , Fe [NT6] (Fig. 9.7) and six cations—sodium (Na ), nitrosocyanaminium CAm), ammonium (NH4 ), hydrazonium (Hyzm), l,2,5-triamino-l,2,3-triazolium (TATm) and 5-amino-l-nitroso-l,2,3,4-tetrazolium (ANTm) were reported (Fig. 9.8) [53]. 

The primaiy explosives prepared from the above-mentioned cations and anions are sparingly soluble in most common organic solvents and water, are moisture and light resistant, and thermally stable up to 250 C. The densities of some of the candidates are summarized in Table 9.9. 

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Kinetics of aquation of iron(n) complexes of 2,2 -bipyridyl, 1,10-phenan-throline, and their substituted derivatives have been much studied in water, less so in mixed aqueous solvents. Whereas the rate of aquation of [Fe(4,7-diPh-phen)3] + in acidic aqueous solution is approximately independent of the nature of the acid added, solutions of this complex in methanol solvolyse at rates which depend markedly on the nature of the acid added. A similar phenomenon has been observed for the aquation of [Fe(phen)a] +, [Fe(5-NOa-phen)3] +, and [Fe(4,7-diMe-phen)a] + in dioxan-water mixtures. These effects have been variously ascribed to the different strengths of the various acids i and to ion-pair formation. It is interesting that the rates of aquation of the iron(n) complexes in aqueous dioxan decrease as the concentration of acid increases when the acid added is perchloric or sulphuric. As ion pairs between complex cations and simple anions are generally more reactive than the free complexes, the observed rate trend is ascribed here, as in a similar situation involving the complexes [M(NH3)6(NOa)] +, with M = Rh or Ir, to the decrease in water activity on adding electrolytes. ... 

The most popular device for fluoride analysis is the ion-selective electrode (see Electro analytical techniques). Analysis usiag the electrode is rapid and this is especially useful for dilute solutions and water analysis. Because the electrode responds only to free fluoride ion, care must be taken to convert complexed fluoride ions to free fluoride to obtain the total fluoride value (8). The fluoride electrode also can be used as an end poiat detector ia titration of fluoride usiag lanthanum nitrate [10099-59-9]. Often volumetric analysis by titration with thorium nitrate [13823-29-5] or lanthanum nitrate is the method of choice. The fluoride is preferably steam distilled from perchloric or sulfuric acid to prevent iaterference (9,10). Fusion with a sodium carbonate—sodium hydroxide mixture or sodium maybe required if the samples are covalent or iasoluble. 

These results indicate that in the polymerisation of styrene by perchloric acid the propagating species is not a carbonium ion (either free or paired), but a complex between acid and monomer. Our results indicate that this has the composition HC104, 4C8H8 and that it participates in the equilibrium... 

An interesting alternative to the use of chromium(VI) oxidants for the conversion of 1 to 2 involves the use of a low-valent iron reagent prepared in situ by the action of hydrogen peroxide on an iron(II) complex of 1 (73). Vinblastine (as the free base) is treated with 2 equiv of perchloric acid in acetonitrile at -20°C. Ferrous perchlorate is then added, followed by the addition of excess 30% hydrogen peroxide. Work-up of the reaction mixture with a saturated solution of ammonium hydroxide gives 2 in yields of 35-50% after chromatography. 

Complexes of zinc chloride and perchlorate with the carcinogenic N, A -/3-chloroethyl-ethylenediamine have been reported.1218 The solvolysis rates of the free ligand and of the zinc complex have been studied by NMR spectroscopy. 

One of the most spectacular and useful template reactions is the Curtis reaction , in which a new chelate ring is formed as the result of an aldol condensation between a methylene ketone or inline and an imine salt. The initial example of this reaction was the formation of a macrocyclic nickel(II) complex from tris(l,2-diaminoethane)nickel(II) perchlorate and acetone (equation 53).182 The reaction has been developed by Curtis and numerous other workers and has been reviewed.183 In mechanistic terms there is some circumstantial evidence to suggest that the nucleophile is an uncoordinated aoetonyl carbanion which adds to a coordinated imine to yield a coordinated amino ketone (equation 54). If such a mechanism operates then the template effect is largely, if not wholly, thermodynamic in nature, as described for imine formation. Such a view is supported by the fact that the free macrocycle salts can be produced by acid catalysis alone. However, this fact does not... 

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