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Influence of oxidation state of sulfur on the dissociation of [Tz‐(CH 2 ) n ‐S(O) m ‐(CH 2 ) n ‐Tz + Na + ] adducts generated by electrospray ionization (Tz = tetrazole ring; n = 2, 3; m = 0, 1, 2)
Author(s) -
Oliveira Sheila Rodrigues,
Nogueira Luciano José,
Augusti Rodinei,
Resende Stoianoff Maria Aparecida,
Aguilar Charles Martins,
Rocha Willian Ricardo,
Donnici Claudio Luis
Publication year - 2011
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.5338
Subject(s) - chemistry , sulfoxide , sulfone , adduct , medicinal chemistry , dissociation (chemistry) , organosulfur compounds , tetrazole , fragmentation (computing) , sulfur , stereochemistry , photochemistry , organic chemistry , computer science , operating system
Sodium adducts of six organosulfur‐α,ω‐ditetrazole compounds (Tz‐(CH 2 ) n ‐S(O) m ‐(CH 2 ) n ‐Tz; where Tz = tetrazole ring; n = 2, 3; m = 0, 1, 2) were generated via electrospray ionization (ESI) and their fragmentation pattern assessed via collision‐induced dissociation (CID). Two main dissociation channels were observed: (a) losses of N 2 and HN 3 from the tetrazole rings; (b) cleavage of the C–S bond. The sulfoxides pass predominantly through the second fragmentation pathway, but for the sulfides and sulfones the tetrazole ring fragmentation occurs. Theoretical calculations at the B3LYP/6‐31 + G(d,p) level indicate that for all the adducts (sulfide, sulfoxide, and sulfone) the dissociation pathway that leads to product ions arising from loss of N 2 was the most exothermic. Based on these results and assumptions, it was postulated that the dissociation of the sulfoxide adducts occurs under kinetic control (N 2 ‐loss pathway via a much more energetic transition state). For the sulfide and sulfone adducts, on the other hand, the dissociation process takes place via a thermodynamically controlled process. Copyright © 2011 John Wiley & Sons, Ltd.