Abstract
The cyanate anion (OCN)- may be formed in the ion source of a reverse sector VG ZAB 2HF mass spectrometer by dissociative electron capture of phenyl cyanate (PhOCN). The isomeric fulminate anion (ONC)- is formed by (i) deprotonation of nitromethane (with HO-) followed by elimination of H2O (-CH2NO2 → [(CHN(O)(OH)]- → (ONC)- + H2O) and (ii) the reaction between CH2NOCH3 and O•- [CH2NOCH3 + O•- → (ONC)- + H2O + CH3•]. Neutralization of the cyanate and fulminate anions by Franck−Condon vertical one-electron oxidation (in the first of two tandem collision cells of the mass spectrometer) yields the cyanate (OCN) and fulminate (ONC) radicals, both of which are stable for at least 1 μs. Ionization of these neutrals by one-electron oxidation in a second collision cell produces the cyanate and fulminate cations. A proportion of each of these cations undergoes isomerization. Theoretical and experimental studies show that (i) these rearrangements involve the less stable singlet forms of the cations, (ii) the cationi...
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