TY - JOUR
T1 - Mass spectrometric studies of azides
T2 - Reactions of Ar + with 3-azidopropionitrile, 2-azidopropionitrile, and azidoacetonitrile in a Fourier transform ion cyclotron resonance mass spectrometer
AU - Barros, Maria Teresa
AU - Beyer, Martin K.
AU - Costa, Maria Lourdes S.L.
AU - Duarte, Maria Filomena
AU - Fernandez, Maria Tereza
AU - Martins, Filipa T.
AU - Rodrigues, Paula R. S.
AU - Watts, Peter
PY - 2004/9
Y1 - 2004/9
N2 - The reactions of Ar + with 3-azidopropionitrile, 2-azidopropionitrile, and azidoacetonitrile have been studied in a Fourier transform ion cyclotron resonance mass spectrometer. The dominant and, in the case of 2-azidopropionitrile the only, primary reaction is charge transfer although the resultant molecular ion immediately fragments. In the cases of 3-azidopropionitrile and azidoacetonitrile a small amount of hydrogen abstraction to form ArH + occurs. In addition to the unambiguous identification of the molecular formula of the product ions leading in most cases to suggested chemical structures with known proton affinities, the time profiles of the product ions were determined and kinetic analysis allowed the primary product ions to be differentiated from the secondary product ions. Many secondary reactions of the primary ions with the parent neutral molecule occur, the majority initiated by proton transfer. Some of them lead to fragmentation but others to the protonated azidonitrile. A comparison with a recently published account of the EI fragmentation of the same three azidonitriles leads to the suggestion that Ar + chemical ionisation is potentially more appropriate for investigating the decomposition of fragile molecules such as the azidonitriles than is EI.
AB - The reactions of Ar + with 3-azidopropionitrile, 2-azidopropionitrile, and azidoacetonitrile have been studied in a Fourier transform ion cyclotron resonance mass spectrometer. The dominant and, in the case of 2-azidopropionitrile the only, primary reaction is charge transfer although the resultant molecular ion immediately fragments. In the cases of 3-azidopropionitrile and azidoacetonitrile a small amount of hydrogen abstraction to form ArH + occurs. In addition to the unambiguous identification of the molecular formula of the product ions leading in most cases to suggested chemical structures with known proton affinities, the time profiles of the product ions were determined and kinetic analysis allowed the primary product ions to be differentiated from the secondary product ions. Many secondary reactions of the primary ions with the parent neutral molecule occur, the majority initiated by proton transfer. Some of them lead to fragmentation but others to the protonated azidonitrile. A comparison with a recently published account of the EI fragmentation of the same three azidonitriles leads to the suggestion that Ar + chemical ionisation is potentially more appropriate for investigating the decomposition of fragile molecules such as the azidonitriles than is EI.
KW - Ar
KW - Azidonitriles
KW - Fragmentations
KW - FTICR
KW - Ion-molecule reactions
KW - Mass spectrometry
UR - http://www.scopus.com/inward/record.url?scp=4344624711&partnerID=8YFLogxK
U2 - 10.1016/j.ijms.2004.06.012
DO - 10.1016/j.ijms.2004.06.012
M3 - Article
VL - 237
SP - 65
EP - 73
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
SN - 1387-3806
IS - 1
ER -