CONTINUING THE SEARCH FOR A NONCLASSICAL ETHYL CATION STABILIZED BY ORGANIC-MOLECULES - THE TRIETHYLOXONIUM ION

Triethyloxonium ions, (C2H5O+, and their deuterated analogues were pro duced in a tandem mass spectrometer and a Fourier transform ion cyclot ron resonance mass spectrometer by ion-molecule reactions in mixtures of ethyl iodide and diethyl ether. Three ion-molecule reactions were i dentified 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 isom er was also generated by the dissociation of the ionized adduct, [(C2H 5)(2)(OIC2H5)-I-.]](+.). Only C2H4 loss from ions produced by reaction (3) showed H-D mixing in the ethyl group originally attached to iodin e atom. No firm evidence was found for the participation of a non-clas sical H-bridged ion.