Continuing the search for a non-classical ethyl cation stabilized by organic molecules; The triethyloxonium ion

Triethyloxonium ions, (C2H5O+, and their deuterated analogues were produced in a tandem mass spectrometer and a Fourier transform ion cyclotron resonance mass spectrometer by ion-molecule reactions in mixtures of ethyl iodide and diethyl ether. Three ion-molecule reactions were identified as the sources of (C2H5O+, namely (C2H5)(2)O-+. + C2H5I --> (C2H5O+ + I-. (1), (C2H5)(2)OH+ + C2H5I --> (C2H5O+ + HL (2) and C2H5I+. + (C2H5)(2)O --> (C2H5)(2)O+(*C2H5) + I-. (3). Reactions (1) and (3) produced stable intermediate adducts; (2) did not, Metastable (C5H5O+ ions formed by all these reactions lost C2H4. Ions from reactions (1) and (3) were proposed to have the classical structure, and this isomer was also generated by the dissociation of the ionized adduct, [(C2H5)(2)(OIC2H5)-I-.]](+.). Only C2H4 loss from ions produced by reaction (3) showed H-D mixing in the ethyl group originally attached to iodine atom. No firm evidence was found for the participation of a non-classical H-bridged ion.