Azide cation

Sodium azide from Wako Pure Chemical Ind., Japan, was used without puri fi cation. 

MesSiNs yields (SN)x as a black solid. By contrast, the explosive and insoluble black compound SesNaCla, which probably contains the [SesNaCl]" cation, is prepared by the treatment of SeaCla with trimethylsilyl azide in CH2CI2 (Eq. 2.13). ... 

Chalcogen-nitrogen cations can be generated by the reactions of homopolyatomic chalcogen cations with azides. For example, the... 

The cyclocondensation of trimethylsilyl azide with a bis(sulfenyl chloride) is an efficient synthesis of dithiazolium cations (Section 11.3.5) (Eq. 2.15). ... 

The yellow [S4N5] anion (5.26) was first reported in 1975 from the methanolysis of Me3SiNSNSiMc3. It can also be prepared by the treatment of S4N4 with certain nucleophiles, e.g., secondary amines or azide salts of small alkali metal cations (Eq. 5.16). The reaction of (NSC1)3 with dry liquid ammonia at -78°C also generates [NH4][S4N5] in ca. 50% yield." ... 

N3S3F2][MF6] can be isolated from the reaction of 8.12b with MF5 (M = As, Sb), but they decompose to give the bicyclic cation [S4N5] (Section 5.3.8). Treatment of 8.12a with trimethylsilyl azide generates the polymer presumably via the intermediate formation of... 

Nitrogen forms more than 20 binaiy compounds with hydrogen of which ammonia (NH3, p. 420), hydrazine (N2H4, p. 427) and hydrogen azide (N3H, p. 432) are by far the most important. Hydroxylamine, NH2(OH), is closely related in structure and properties to both ammonia, NH2(H), and hydrazine, NH2(NH2) and it will be convenient to discuss this compound in the present section also (p. 431). Several protonated cationic species such as NH4+, N2H5+, etc, and deprotonated anionic species such as NH2 , N2H3 , etc. also exist but ammonium hydride, NH5, is unknown. Among... 

Acyl azide, amines from, 935 Acyl carrier protein, function of, 1 140 Acyl cation, electrostatic potential map of, 558... 

DNA sequencing and. 1113 Electrospray ionization (ESI) mass spectrometry, 417-418 Electrostatic potential map, 37 acetaldehyde, 688 acetamide, 791,922 acetate ion. 43. 53, 56, 757 acetic acid. 53. 55 acetic acid dimer, 755 acetic anhydride, 791 acetone, 55, 56. 78 acetone anion, 56 acetyl azide, 830 acetyl chloride, 791 acetylene. 262 acetylide anion, 271 acid anhydride, 791 acid chloride, 791 acyl cation, 558 adenine, 1104 alanine, 1017 alanine zwitterion, 1017 alcohol. 75 alkene, 74, 147 alkyl halide, 75 alkyne. 74... 

Mercury, tris( 1,10-phenanthroline)-structure, 1, 64 Mercury acetate, S, 1066 Mercury azide, 5, 1062 Mercury bromide, S, 1059 Mercury cations Hg ... 

Interestingly, no SO 2 was evolved in this reaction as in the photolysis of a-toluenesulphonyl azide. This could be explained on the basis of a cation-radical anion pair which collapses as in Eq, (8) to give a sulphon-amido radical, and no free nitrene is formed 21>. 

Petrie, M. A. et al., J. Amer. Chem. Soc., 1997, 119, 8802 All salts of this cation were friction and shock sensitive, too sensitive for actual use as explosives. The most sensitive though, with estimated energy of 5.4 kJ/g, not the most powerful, was the perchlorate. Even though prepared on low milligram scale this invariably detonated spontaneously during work-up or soon after. The more powerful dinitramide (5.8 kJ/g) decomposed non-explosively on standing. See other ORGANIC AZIDES... 

Schleyer, P. von R. et al., Angew. Chem. (Int.), 1992, 31(10), 1338 This compound, which is more sensitive than iodonium azide, can explode spontaneously below —20°C. It is the first known I-N containing cationic species. 

Electrophilic addition to spiro phosphenium cations 258 provides a route to spirophosphoranes. However, only very active electrophiles are suitable, for example, benzenesulfonyl azide which on reflux in acetonitrile with 258 yields 259 (Equation 70) <1998RJC530>. 

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