|Title||Generation and chemistry of fluorinated acetoxyl and oxyallyl biradical anions (distonic radical anions) in the gas phase|
|Publication Type||Journal Article|
|Year of Publication||1996|
|Authors||M.L. Zhong, M.L. Chabinyc, and J.I. Brauman|
|Journal||JOURNAL OF THE AMERICAN CHEMICAL SOCIETY|
|Date Published||DEC 11|
Electron impact on fluorinated acetyl compounds RCOF(3) (R=OH, OSi(CH3)(3), OCH3, CF3COCH2, CH3COCH2, CH3, 3,5-(CF3)(2)C6H3CH2) in an FT-ICR spectrometer yields ionic products of m/z=[M-HF]. These products are proposed to arise via a two-step mechanism: upon electron impact the neutral precursor gives a fluoride ion-neutral radical complex followed by a secondary reaction of the fluoride anion with the neutral radical, either nucleophilic substitution or proton transfer, to yield a biradical anion (distonic radical anion). These radical anions were isolated and their chemical properties were studied. They undergo reactions characteristic of closed-shell anions, e.g. proton transfer, or characteristic of open-shell species, e.g. radical addition-elimination reactions.