Matrix Isolation, Zero-Field Splitting Parameters, and Photoreactions of Septet 2,4,6-Trinitrenopyrimidines

• Published in: Journal of organic chemistry Vol. 79; no. 13; pp. 6047 - 6053
• Main Authors: Chapyshev, Sergei V, Ushakov, Evgeny N, Neuhaus, Patrik, Sander, Wolfram
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03-07-2014
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo500677g

The key intermediates of decomposition of high-energy 2,4,6-triazidopyrimidine and its 5-chloro-substituted derivative, the detonation of which is used for preparation of carbon nitrides, were investigated using electron paramagnetic resonance (EPR) spectroscopy in combination with quantum chemical calculations. The decomposition of the triazides was carried out photochemically, using the matrix isolation technique. The photodecomposition of both triazides with 254 nm light in argon matrices at 5 K occurred selectively to subsequently give the corresponding triplet 4,6-diazido-2-nitrenopyrimidines, quintet 4-azido-2,6-dinitrenopyrimidines, and septet 2,4,6-trinitrenopyrimidines. The latter were photochemically unstable and decomposed to form triplet nitrenes NCN and NNC as well as triplet carbenes NCCCN, HCCN, and HCCCCN. The results obtained provide important information about exchange interactions in high-spin nitrenes with the pyrimidine ring and the mechanism of the formation of carbon nitrides during thermolysis of 2,4,6-triazidopyrimidine.