- Fluorine shifts in gaseous cations. Analogues of Wagner-Meerwein rearrangements
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In the gas phase ionized (CH3)2CFCH2OPh (where the asterisk designates a 13C-label) decomposes to yield ionized phenol via two competing pathways, both of which pass through intermediate ion-neutral complexes. One pathway involves methyl shift, which produces complexes that contain 2-fluorobutyl cations. The other pathway involves fluorine transposition, which forms complexes containing fluoro-tert-butyl cations. The distribution of 13C in the recovered neutral fluoroalkenes confirms that fluorine migration has indeed taken place, and SCF computations point toward a bridged, three-member cyclic transition state. Ab initio calculations provide an ordering of C4H8F+ structures, some of which are isoelectronic with C4H8O epoxy and carbonyl compounds, as well as those that have no stable isoelectronic neutral counterparts.
- Shaler, Thomas A.,Morton, Thomas Hellman
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p. 9222 - 9226
(2007/10/02)
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