Abstract
The application of the continuous ejection technique to observe unimolecular dissociation of metastable organometallic ions in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer is demonstrated. A radio-frequency ejection voltage is continuously applied at a frequency corresponding to the exact mass of a metastable adduct ion, [MC6H6+]* (M = Cr and Mn), formed in the reactions of Cr+ and Mn+ with C6H6. By monitoring the initial metal ion intensity as a function of ion ejection time, metastable ion lifetimes and unimolecular dissociation rate constants are obtained. The bond dissociation energies D0(Cr+−C6H6) = 1.75 ± 0.1 eV and D0(Mn+−C6H6) = 1.50 ± 0.1 eV are derived from RRKM modeling and are in excellent agreement with other literature values.
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