Competitive charge-remote and anion-induced fragmentations of the non-8-enoate anion. A charge-remote reaction which co-occurs with hydrogen scrambling

Dua, S., Bowie, J. H., Cerda, B. A., Wesdemiotis, C., Raftery, M. J., Kelly, J. F., Taylor, M. S., Blanksby, Stephen J., & Buntine, M. A. (1997) Competitive charge-remote and anion-induced fragmentations of the non-8-enoate anion. A charge-remote reaction which co-occurs with hydrogen scrambling. Journal of the Chemical Society-Perkin Transactions 2, pp. 695-702.

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The non-8-enoate anion undergoes losses of the elements of C3H6, C4H8 and C6H12 on collisional activation, The mechanisms of these processes have been elucidated by a combination of product ion and labelling (H-2 and C-13) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of 'C4H8' is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of 'C6H12' occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-l-ene and hex-l-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-l-ene and hex-l-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above].

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9 citations in Web of Science®
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ID Code: 71640
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: gas-phase, neutralization-reionization, energy-requirements, synchronous-transit, negative-ions, decompositions, rearrangement, carbanions, states
DOI: 10.1039/a607437e
ISSN: 0300-9580 (online) 1472-779X (print)
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 1997 Royal Society of Chemistry
Deposited On: 21 May 2014 03:35
Last Modified: 21 Jun 2017 09:01

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