Azides silyl

Organoboranes react with a mixture of aqueous NH3 and NaOCl to produce primary amines. It is likely that the actual reagent is chloramine NH2CI. Chloramine itself,hydroxylamine-O-sulfonic acid in diglyme, and trimethyl-silyl azide " also give the reaction. Since the boranes can be prepared by the hydroboration of alkenes (15-16), this is an indirect method for the addition of NH3 to a double bond with anti-Markovnikov orientation. Secondary amines can be prepared by the treatment of alkyl- or aryldichloroboranes or dialkylchlorobor-anes with alkyl or aryl azides. 

In contrast to diazido compounds [102] and [104], which throw off two azido groups and form silylene and germylene, photodecomposition of silyl azide [105] led to the generation of aminosilylene [107] via isomerization of initially formed nitrene [106] (Maier et al., 1989b). The IR spectrum of the... 

Some cycloaddition reactions of 4 are summarized in Scheme 1. This shows that silylene 4 undergoes reactions with nitriles [14], phosphaalkynes [15], silyl azides [16], diazabutadienes [17], 2,2 -bipyridyl and its derivatives [18, 19], a-ketoimines [19], and pyridine-2-aldimines [19]. 

Both terminal and internal BENAs (434) are readily subjected to this transformation to give the a-azido oximes (465) in very high yields. The improved procedure allows one to prepare compounds (465) virtually without by-products. The use of a large excess of silyl azide and the presence of small additives of triethylamine (5%) are of principal importance. 

Scheme 6.38. Cr-catalyzed asymmetric addition of silyl azides to meso epoxides.

Quite a number of new Fcg clusters has resulted from unusual reactions. Among these are the nitrogen bridged triangles [26] prepared from Fe2(CO)9 and silyl azides (31, 255) and [37] prepared from Fe2(CO)g and several azo compounds (24, 25), while the previously known clusters Fe3(CO)9(NR)2 were prepared from Fe(CO)5 and organic nitro compounds (26). 

Synthesis of Primary Amines via the Reaction of Organoboranes with Trimethyl silyl Azide in Neutral Medium 2-exo-Norbornyl Amine. 

However, one typical example of a silane, alkyl-substituted silane, silyl azide, silyamine, siloxane and a silane polysulfide polymer, which is or can possibly be used in ordn areas, is presented next. Substituted siloxanes are defined and presented separately under Silicones ... 

Silyl Azides. Many of these compns are extremely unstable and several of the aryl substituted compds such as phenyltriazidosilane (C6HsN9Si) deton on handling (Refs 17 18). 

Silyl Azides. See under Silyl Azides in this... 

Alkenylsilanes react with silyl azide and other organic azides to give bissilylenamines and silylaziridines, respectively, via unstable triazoline intermediates.78 Heating trimethylsilyl azide with cyclohexene or vinyltrieth-ylsilane for 10 days affords a modest yield of the respective aziridine,178 but with carefully purified trimethylsilyl azide, even after 2 weeks of reflux, no olefin consumption is indicated.104 Unstable triazoline intermediates are also formed from the reaction of cyanogen azide,808 picryl azide,29 and arylsulfonyl azides808 with unactivated olefinic bonds. 

When deuteriated 92 is generated from irreversibly decomposing precursors, just the head-to-tail dimer [(D3C)2Si—C(SiMe3)2]2 is found97. An even faster reaction than the methyl migration is the reaction of the silene with silyl azides. Just one of the possible... 

The ideal starting compound for the matrix studies of the parent silanitrile, H—Si=N, is silyl azide 734. By judicious choice of irradiation wavelengths the preparation and interconversion of a series of H,Si,N containing species 735-737, characterized by UV and IR spectra, was possible. It was found that silanitrile 733 can indeed be obtained, at first in a mixture with the hydrogen associate 733 H2. Tempering the matrix to 30 K leaves only 733. The interconversion of 737 and 733 is also possible (equation 242). 

Azido alcohols.1 This azide is considerably more reactive for cleavage of epoxides than azidotrimethylsilane, which requires a Lewis acid promotor. Although DMF enhances the reactivity of the silyl azide, it lowers the reactivity of the stannyl azide. The reactivity of the latter azide is also decreased by neighboring ester, acetonide, or ether groups. 

Ogilvie, J. F., and S. Cradock Spectroscopic Studies of the Photodecomposition of Silyl Azides in Argon Matrices near 4 K Detection of Iminosilicon, HNSi. Chem. Commun. 1966, 364—365. 

The orange complex is air sensitive in the solid state. It is reasonably soluble and stable in THF but decomposes in nonpolar solvents, such as benzene, to give polymeric halogen-bridged products.9 It is paramagnetic with a magnetic moment of 3.63 BM, and its IR spectrum shows a very intense band at about 820 cm-1 due to coordinated THF. Its reactions with tertiary phosphines in THF give a series of molybdenum (III) tertiary phosphine complexes,9 and with trimethyl-silyl azide Mo(V) nitrido complexes are formed.8... 

From metal hydrides (//i) or alkyls 40) and aryl or silyl azides. 

The compounds of this class, mostly silyl derivatives (R = SiMes), prepared by Staudinger reactions from the corresponding diphosphines and silyl azides (Scheme 39), received recent attention owing to their versatility as nitrogen-donor ligands. ... 

In contrast, the reaction between sterically normal silyl azides and metal organyls (the same is true for germyl and stannyl azides) leads either to substitution of the silicon-bound azide group by an organyl group, or to cleavage of molecular nitrogen from the azide moiety 10) [Eq. (3)]. The preference for reaction in paths (a) or (b) of Eq. (3) depends on the kind... 

---