Trifluoromethylsulfonate (triflate) and bis(trifluoromethylsulfonyl)imide (triflimide) salts, well-known Lewis acid catalysts, present some difficulty in their characterization. By using nitromethane as the solvent, useful electrospray mass spectra in positive and negative ion mode were obtained for salts of metals in oxidation states +2 and +3. In positive mode, addition of a strong Lewis base (triphenylphosphine oxide, TPPO), capable of displacing a triflate (TfO(-)) or a triflimide (Tf(2)N(-)) anion, is necessary for obtaining useful spectra. Under these conditions of solvent and added ligand, the most abundant ions were [M(2+)(A(-))(TPPO)(2)](+) or [M(3+)(A(-))(2)(TPPO)(2)](+) with A(-) = TfO(-) or Tf(2)N(-). The MS/MS spectra of these diagnostic ions provide additional analytical information. The breakdown curves, in the form of % dissociated as a function of the ion activation energy, offer a mean for investigating the bonding in these ions.
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