Premium
Bond dissociations in hypervalent ammonium radicals prepared by collisional neutralization of protonated six‐membered nitrogen heterocycles
Author(s) -
Wolken Jill K.,
Nguyen Viet Q.,
Tureček František
Publication year - 1997
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199711)32:11<1162::aid-jms571>3.0.co;2-5
Subject(s) - chemistry , hypervalent molecule , radical , medicinal chemistry , bond cleavage , dissociation (chemistry) , ammonium , photochemistry , protonation , octane , organic chemistry , ion , reagent , catalysis
Hypervalent organic ammonium radicals were generated by collisional neutralization with dimethyl disulfide of protonated 1,4‐diazabicyclo[2.2.2]octane (1H + ), N,N′‐dimethylpiperazine (2H + ) and N‐methylpiperazine (3H + ). The radicals dissociated completely on the 5.1 μs time‐scale. Radical 1H • underwent competitive N−H and N−C bond dissociations producing 1,4‐diazabicyclo[2.2.2]octane and small ring fragments. Dissociations of radical 2H • proceeded by N−H bond dissociation and ring cleavage, whereas N−CH 3 bond cleavage was less frequent. Radical 3H • underwent N−H, N−CH 3 and N−C ring bond cleavages followed by post‐reionization dissociations of the formed cations. The pattern of bond dissociations in the hypervalent ammonium radicals derived from six‐membered nitrogen heterocycles is similar to those of aliphatic ammonium radicals. © 1997 John Wiley & Sons, Ltd.