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First Synthesis and Investigation of Two Hydroxyalkyl‐Substituted 2‐Tetrazenes
Author(s) -
Porath Bernd,
Münzenberg Ralf,
Heymanns Peter,
Rademacher Paul,
Boese Roland,
Bläser Dieter,
Latz Rüdiger
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199807)1998:7<1431::aid-ejoc1431>3.0.co;2-m
Subject(s) - chemistry , hydrogen bond , intermolecular force , molecule , ab initio , crystallography , atoms in molecules , computational chemistry , hydrogen , nitrogen , ab initio quantum chemistry methods , organic chemistry
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, 1 H NMR, 15 N NMR) and theoretical methods. The structures of 1a and its bis(trimethylsilyl) 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‐ 15 N 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.