First Synthesis and Investigation of Two Hydroxyalkyl-Substituted 2-Tetrazenes

✍ Scribed by Bernd Porath; Ralf Münzenberg; Peter Heymanns; Paul Rademacher; Roland Boese; Dieter Bläser; Rüdiger Latz

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 434 KB
• Volume: 1998
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199807)1998:7<1431::aid-ejoc1431>3.0.co;2-m

✦ Synopsis

Two members of previously unknown hydroxyalkyl-2-intermolecular hydrogen bonding to a larger extent than the azo nitrogen atoms; the corresponding energy difference of tetrazenes (1a, 2a) have been synthesized and hydrogen bonding of these novel difunctional compounds has been the two types of hydrogen bonds is about 3 kJ mol -1 . The hydrogen bonds can either stabilize or destabilize 2-investigated by spectroscopic (IR, 1 H NMR, 15 N NMR) and theoretical methods. The structures of 1a and its tetrazenes thermodynamically depending on which nitrogen atoms are involved. Complexation of 1,1,4,4-tetramethyl-2-bis(trimethylsilyl) derivative 1b were determined by X-ray analysis. In the crystalline state, molecules 1a are associated tetrazene with methanol is accompanied by only minor changes in geometric parameters whereas systematic effects by O-H•••O hydrogen bonds that form a three-dimensional network. Ab initio HF and DFT as well as semiempirical SCF on the electronic structure are more distinct. Transition states for N-N bond cleavage are stabilized to a larger extent calculations show that O-H•••N hydrogen bonds of 2tetrazenes are medium strong. The δ-15 N data and the making such compounds rather sensitive for thermal decomposition. quantum chemical calculations indicate that the amino nitrogen atoms of a 2-tetrazene are involved in