Fragmentations of deprotonated alkyl hydroperoxides (ROO-) upon collisional activation : A combined experimental and computational study

Blanksby, Stephen J., Kato, S., Bierbaum, V. M., & Ellison, G. B. (2003) Fragmentations of deprotonated alkyl hydroperoxides (ROO-) upon collisional activation : A combined experimental and computational study. Australian Journal of Chemistry, 56(5), pp. 459-472.

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The collision-induced dissociation ( CID) mass spectra of the [M-H](-) anions of methyl, ethyl, and tert-butyl hydroperoxides have been measured over a range of collision energies in a flowing afterglow - selected ion flow tube (FA-SIFT) mass spectrometer. Activation of the CH3OO- anion is found to give predominantly HO- fragment anions whilst CH3CH2OO- and (CH3)(3)COO- produce HOO- 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 alpha-carbon in the case of CH3OO- or the beta-carbon for CH3CH2OO- and (CH3)(3)COO-. Electronic structure calculations suggest that for the CH3CH2OO- anion, which can theoretically undergo both alpha- and beta-proton abstraction, the latter pathway, resulting in HOO- + CH2CH2, is energetically preferred.

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11 citations in Web of Science®
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ID Code: 71926
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: tandem mass-spectrometry, gas-phase acidity, photoelectron-spectroscopy, lipid hydroperoxides, flowing afterglow, peroxyl radicals, diacyl, peroxides, thermochemistry, decomposition, anions
DOI: 10.1071/ch03039
ISSN: 1445-0038 (online) 0004-9425 (print)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2003 CSIRO
Deposited On: 26 May 2014 02:43
Last Modified: 05 Jan 2016 04:19

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