Ferrocenyl azide

Ferrocenyl azide with various RMgX reagents yielded the triazenes... 

Other aminoferrocene precursors are Af-ferrocenyl phthalimide, which can be converted to FC-NH2 by N2H4 H2O in boiling ethanol (82% yield) [16, 44], and ferrocenyl azide, FC-N3, which has been reduced with LiAlH4 (72% yield) (cf. Scheme 5-6) [45]. Ferrocenyl amine, FC-NH2, is generally formed among other products in the thermal or photochemical decomposition of FC-N3 [56] and in the thermolysis of ferrocenyl isocyanate, Fc-NCO [57], in solvents such as cyclohexane, cyclohexene and benzene, probably by reaction of the intermediate nitrene, [Fc-N], with the solvent [56, 57]. The reduction of nitroferrocene, FC-NO2, provides another route to aminoferrocene, FC-NH2 [58 — 61] however, FC-NO2 is not an easily accessible starting material. 

The variation in frequencies and integrated intensities of the N3 bands were discussed in relation to the nature of the radical R. The azide group was considered to act either as a donor or acceptor of electron (section I.A), depending on R. (However the variation in v is small compared to the scatter of results in literature.) The conditions for Fermi interaction appear to be hindered by a barrier such as Fe atom in ferrocenyl azide. 

Azidoferrocenes have been synthesized by treating bromoferrocenes with azide ion and cupric bromide in dimethylformamide . Thus ferrocenyl azide (165) was obtained in 98% yield from bromoferrocene and 1, T-ferrocenylene diazide (166) was prepared from the corres-... 

The thermal decomposition of ferrocenyl azide in benzene gave ferrocene (13 6%), phenylferrocene (1 9%), azoferrocene (17 8%), and ferroccnylamine (16-9%) Thermolysis of this azide in cyclohexane gave ferrocene (7 3%), and azoferrocene (20 5%). No product of aliphatic G—H insertion nor of aromatic substitution by the nitrene was observed (For more results and a comparison with photolysis, see section V.B.). 

Ferrocenyl azide (370) has been photolysed in various solvents in the presence and absence of oxygen The results show that t vo... 

Figure 10.8 Proposed orientation of ferrocenyl azide inside the P-cyclodextrin cavity according to ICD. (A) axial, (B) equatorial arrangement. Reprinted with permission from [70], Copyright 2006 American Chemical Society...

Table 10.7 Yields of isolated products from decomposition of ferrocenyl azide (FCN3IIO) complexes...

P. Walla, V. B. Arion, U. H. Brinker, Solvent- and temperature-tuned orientation of ferrocenyl azide inside jS-cyclodextrin, J. Org. Chem., 2006, 71, 3274-3277. 

Addition of a discrete arylnitrene to an alkene was first reported in 1971 although addition of ethoxycarbonylnitrene to olefins was well documented. Photolysis (or thermolysis) of ferrocenyl azide " (25) in cyclohexene yields the aziridine 26 and the predictable products 27-29. The possibility of triazoline formation prior to nitrogen elimination or concerted addition and elimination from the azide were considered to be very unlikely ... 

Trapping of nitrenes by oxygen has been observed in the deoxygenation of nitrosobenzene, thus leading to nitrobenzene. Photolysis of ferrocenyl azide in benzene or cyclohexane under oxygen provides on of the best methods of preparing nitroferrocene ... 

Figure 12.4 Solid state structures of ferrocenyl azide and , V-ferrocenylene azide...

Similar click protocol was employed for synthesis of ferrocene-based triazolyl glycoconjugates 23 by reacting ferrocenyl azide 22 and terminal sugar-based acetylenic compound 21 under click condition. Resultant ferrocenyl glycoconjugate 23 is supposed to be applicable for the study of protein-carbohydrate interaction using electrochemical biosensing techniques (Scheme 6.7) [23]. 

---