Abstract
Chemical ionization (CI) using the [ClMn(H2O)]+ reagent ion combined with collision-activated dissociation is demonstrated to allow the differentiation of isomeric alkanes (C8H18 and C9H20) and alkenes (C8H16) in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The [ClMn(H2O)]+ ion reacts with each isomeric hydrocarbon molecule to produce a water replacement product [hence providing molecular weight (MW) information], with no accompanying fragmentation. Differentiation of the isomers is achieved on the basis of the different fragmentation patterns observed upon sustained off-resonance irradiation collision-activated dissociation (SORI−CAD) of the isolated water replacement products. Upon activation, the weak bond of the hydrocarbon to ClMn+ is broken. ClMn+ is the major fragment ion for linear alkanes. However, for branched alkanes and all alkenes, the leaving ClMn+ abstracts a weakly bound hydride, an alkyl anion, or an alkene from the hydrocarbon to generate diagnostic carbocation...
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