Gas-Phase Reactions of ClMn(H₂O)⁺ with Polar and Nonpolar Hydrocarbons in a Mass Spectrometer

The gas-phase reactions of ClMn(H 2 O) + with a variety of volatile and nonvolatile, saturated and unsaturated hydrocarbons have been examined by using Fourier transform ion cyclotron resonance mass spectrometry (FT/ICR). The ClMn(H 2 O) + ion reacts rapidly by exclusive H 2 O ligand displacement with all the hydrocarbons studied, including highly branched alkanes that usually fragment upon ionization. These observations are rationalized on the basis of the electronic structure of ClMn + . Collision-activated dissociation of the product ions provides structural information which promises to allow the distinction and structural characterization of isomeric hydrocarbons. These findings suggest that the ClMn(H 2 O) + ion is a highly promising chemical ionization reagent for mass spectrometric characterization of hydrocarbons, including those that commonly exist in petroleum