Gas‐Phase Oxidation (“Charge Stripping”) of Pagodane Radical Cations and Related Cage Hydrocarbons. — A Theoretical‐Experimental Search into Tetramethylene Dications A theoretical screening of the family of tetramethylene dications furnished the open C2h trans configuration as the global minimum. The pagodane dications must owe their stability to the rigidity of their molecular framework. By means of charge‐strip‐Ping mass spectrometry stable dications could be generated for [188.8.131.52]pagodane, its diene valence isomer, and several analogues (including „half‐pagodanes”). Ionization energies for the gas‐phase oxidation of the radical cations were determined. A distinction whether common or isomeric radical cations serve as precursors in the charge stripping reactions could not be achieved due to either the relatively large uncertainties in the determination of the Qmin values or due the fact that in these particular cases charge stripping does not discriminate between structurally closely related hydrocarbon isomers.
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