211613-15-9Relevant academic research and scientific papers
First synthesis and investigation of two hydroxyalkyl-substituted 2-tetrazenes
Porath, Bernd,Muenzenberg, Ralf,Heymanns, Peter,Rademacher, Paul,Boese, Roland,Blaeser, Dieter,Latz, Ruediger
, p. 1431 - 1440 (2007/10/03)
Two members of previously unknown hydroxyalkyl-2-tetrazenes (1a, 2a) have been synthesized and hydrogen bonding of these novel difunctional compounds has been investigated by spectroscopic (IR, 1H NMR, 15N NMR) and theoretical methods. The structures of 1a and its bis(trimethylsily 1) derivative 1b were determined by X-ray analysis. In the crystalline state, molecules 1a are associated by O-H...O hydrogen bonds that form a three-dimensional network. Ab initio HF and DFT as well as semiempirical SCF calculations show that O-H...N hydrogen bonds of 2-tetrazenes are medium strong. The δ-15N data and the quantum chemical calculations indicate that the amino nitrogen atoms of a 2-tetrazene are involved in intermolecular hydrogen bonding to a larger extent than the azo nitrogen atoms; the corresponding energy difference of the two types of hydrogen bonds is about 3 kJ mol-1. The hydrogen bonds can either stabilize or destabilize 2-tetrazenes thermodynamically depending on which nitrogen atoms are involved. Complexation of 1,1,4,4-tetramethyl-2-tetrazene with methanol is accompanied by only minor changes in geometric parameters whereas systematic effects on the electronic structure are more distinct. Transition states for N-N bond cleavage are stabilized to a larger extent making such compounds rather sensitive for thermal decomposition.
