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Studies of the Reaction Behavior of Nitryl Compounds Towards Azides: Evidence for Tetranitrogen Dioxide, N 4 O 2
Author(s) -
Klapötke Thomas M.,
Schulz Axel,
TornieporthOetting Inis C.
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.1491271115
Subject(s) - chemistry , azide , sodium azide , raman spectroscopy , solvent , infrared spectroscopy , medicinal chemistry , photochemistry , organic chemistry , optics , physics
The reaction behavior of NaN 3 , AgN 3 , and Me 3 SiN 3 towards FNO 2 , CINO 2 , NO 2 SbF 6 , and NO 2 BF 4 was investigated. At ‐30°C or below in a solvent‐free system sodium azide did not react with CINO 2 , NO 2 BF 4 , or NO 2 SbF 6 . Below ‐30°C silver azide did not react either with neat C1NO 2 . Treatment of Me 3 SiN 3 with pure C1NO 2 led to the formation of C1N 3 , N 2 O, and Me 3 SiOSiMe 3 . A mechanism for this reaction has been proposed. Pure chlorine azide was isolated by fractional condensation and identified by its low‐temperature Raman spectrum (liquid state). The reaction of Cp 2 Ti(N 3 ) 2 with C1NO 2 also yielded C1N 3 as the only azide‐containing reaction product. Treatment of FNO 2 with NaN 3 at temperatures as low as ‐78°C always ended in an explosion which was probably due to the formation of FN 3 as one of the reaction products. The reaction of NO 2 SbF 6 with NaN 3 in liquid CO 2 (‐55°C· T· ‐35°C) as the solvent afforded a new azide species which was stable at low temperature in solution only and was investigated by means of low‐temperature Raman spectroscopy. The obtained vibrational data give strong evidence for the presence of tetranitrogen dioxide, N 4 O 2 , which can be regarded as nitryl azide (NO 2 N 3 ). The structure and vibrational frequencies of N 4 O 2 were computed ab initio at correlated level (MP2/6‐31 + G * ). In liquid xenon (‐100°C· T· ‐60°C) NaN 3 did not react with NO 2 SbF 6 . A previous literature report on the preparation of N 4 O 2 could not be established.