A tandem mass spectrometric investigation of (C2H5)2X+ ions (X = Cl,Br, I): The involvement of classical and nonclassical ethyl structures therein |
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Authors: | Dmitri V Zagorevskii Sergiu P Palii John L Holmes |
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Institution: | 1. Chemistry Department, University of Ottawa, 10 Marie Curie, K1N 6N5, Ottawa, Ontario, Canada
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Abstract: | The formation of diethyl halonium ions (C2H5)2X+ (X = Cl, Br, I) by a variety of ion-molecule reactions is described. The dissociation characteristics (metastable and collision-induced dissociation mass spectra) of these ions and their isomers were studied in detail. Some of the neutral fragmentation products were examined by their collision-induced dissociative ionization mass spectra. The participation of classical (1, CH3CH2X+CH2CH3) and nonclassical forms of the ions was considered. Dissociation reactions for which loss of positional identity of H-D atoms took place, for example C2H4 loss (a common fragmentation of metastable ions) and C2H5 + formation, were interpreted as involving nonclassical ions, 2. It was concluded that the ion-molecule reactions produced both ion structures, but in different halogen-dependent proportions. For (C2H5)2C1+ ions, 2 is the major species, for (C2H5)2Br+ both 1- and 2-type ions are generated, whereas for (C2H5)2I+ the classical form 1 must be the predominant structure. |
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