94787-56-1Relevant articles and documents
Isolable Adducts of Tertiary Amines and Dinitrogen Trioxide
Rosadiuk, Kristopher A.,Scott Bohle
, p. 4543 - 4549 (2018)
Anhydrous dinitrogen trioxide, N2O3, dissolved in toluene or dichloromethane rapidly forms stable adducts with tertiary amines such triethyl-, tribenzyl-, or trihexyl-amine. With DABCO, 1,4-diazabicyclo[2.2.2]octane it forms a free flowing orange solid. The analytical and spectroscopic data for the DABCO adduct indicate a formula of DABCO(N2O3)2 which has been characterized by IR, Raman, and UV/Vis spectroscopy. The R3N-N2O3 adducts are hydrolytically sensitive oils or solids which rapidly react quantitatively with thiols to give RSNO. The reactivity of the amine adducts is variable, and the products include amine N-oxides, ammonium nitrites, and ammonium nitrates depending upon the adduct, conditions, and substrate. Density functional theory, B3LYP/aug-cc-pvtz, has been used to compare the predicted structures and spectroscopic data for mono and bis adducts. Geometry optimization of the R3N N2O3 adduct gives a weakly bound Lewis acid/base adduct with the amine nitrogen closest to the nitrosyl N with a strongly tilted planar ONNO2 unit.
