
%0 Journal Article
%A Blanksby, Stephen J. 
%A Kato, Shuji 
%A Bierbaum, Veronica 
%A Ellison, G. Barney 
%T Fragmentations of Deprotonated Alkyl Hydroperoxides (ROO<emph type="7">&minus;</emph> Upon Collisional Activation: A Combined Experimental and Computational Study
%J Australian Journal of Chemistry
%D 2003/05/23
%V 56
%N 5
%P 459-472
%K 
%R https://doi.org/10.1071/CH03039
%U https://www.publish.csiro.au/paper/CH03039 
%X The collision-induced dissociation (CID) mass spectra of the [M &minus; H]&#8211; anions of methyl, ethyl, and tert-butyl hydroperoxides have been measured over a range of collision energies in a flowing afterglow&#8211;selected ion flow tube (FA-SIFT) mass spectrometer. Activation of the CH3OO&#8211; anion is found to give predominantly HO&#8211; fragment anions whilst CH3CH2OO&minus; and (CH3)3COO&#8211; produce HOO&#8211; as the major ionic fragment. These results, and other minor fragmentation pathways, can be rationalized in terms of unimolecular rearrangement of the activated anions with subsequent decomposition. The rearrangement reactions occur via initial abstraction of a proton from the &#945;-carbon in the case of CH3OO&#8211; or the &#946;-carbon for CH3CH2OO&#8211; and (CH3)3COO&#8211;. Electronic structure calculations suggest that for the CH3CH2OO&#8211; anion, which can theoretically undergo both &#945;- and &#946;-proton abstraction, the latter pathway, resulting in HOO&#8211; + CH2CH2, is energetically preferred. 
