Abstract
The ion chemistry of the title compounds, a nonafluorobutyl methyl ether and a hydrofluoropropane, is elucidated by a combination of studies using atmospheric pressure ionization mass spectrometry and triple quadrupole mass spectrometry. In the positive ion mode, the hydrofluoroether readily forms an [M−F]+ ion, attributable to hydronium ion induced dehydrofluorination, the product of which can be further hydrated to give a protonated hydrofluoroester. By contrast, the hydrofluoropropane does not react with the hydronium ion but rather gives hydrofluoroalkenylium cations via H atom and F atom abstraction by the dioxygen radical cation. In the negative ion mode, the fluorobutyl methyl ether undergoes dissociative electron capture with O −·2 , O −·2 (H2O), O −·3 , and NO −2 to generate the fluorobutoxy anion, which can dissociate by CF2=O loss to give the perfluorocarbanion when the precursor ions are internally excited. The hydrofluoropropane reacts readily with common atmospheric anions to form molecular complexes with F−, O −·2 , and O −·3 and the strongly H-bonded species, O −·2 (HF) and F−(HF). Interestingly, isomeric pentafluoropropanes form in the reaction with O −·2 , either O −·2 (HF) or F−(HF), depending on the specific pattern of the fluoro substitution.
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Published online May 25, 2005
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Marotta, E., Paradisi, C. & Cooks, R.G. Novel CFCs-substitutes recommended by EPA (hydrofluorocarbon-245fa and hydrofluoroether-7100): Ion chemistry in air plasma and reactions with atmospheric ions. J Am Soc Mass Spectrom 16, 1081–1092 (2005). https://doi.org/10.1016/j.jasms.2005.02.021
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DOI: https://doi.org/10.1016/j.jasms.2005.02.021