Search for charge-remote reactions of even-electron organic negative ions in the gas phase. Anions derived from disubstituted adamantanes
Date
1998
Authors
Dua, S.
Bowie, J.
Cerda, B.
Wesdemiotis, C.
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Advisors
Journal Title
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Volume Title
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Journal article
Citation
Journal of the Chemical Society, Perkin Transactions 2, 1998; 2(6):1443-1448
Statement of Responsibility
Dua, Suresh; Bowie, John H.; Cerda, Blas A.; Wesdemiotis, Chrys
Conference Name
DOI
Abstract
The collision induced decompositions of 3-substituted adamantanecarboxylate anions have been studied with a view to uncover charge-remote fragmentations of the 3-substituent. The 3-substituent is chosen so that it cannot approach the anion site and therefore any fragmentations of that substituent should proceed independently of the charged centre, (i) Charge-remote radical losses are observed from a 3-CH(Et)<inf>2</inf> substituent [e.g. Eṫ and ̇CH(Et)<inf>2</inf> losses], but the classical Adams-Gross charge remote loss of an ethene plus dihydrogen is not observed, (ii) Charge-remote loss of MeOD is observed from a 3-C(CD<inf>3</inf>)<inf>2</inf>(OMe) substituent together with a number of charge-remote radical losses [e.g. Mė, MeȮ and ̇C(CD<inf>3</inf>)<inf>2</inf>(OMe)]. (iii) The 3-substituent C(CD<inf>3</inf>)<inf>2</inf> (OCH=O) undergoes charge-remote loss of HCO<inf>2</inf>D for both the carboxylate anion and its corresponding cation, a neutral reaction analogous to both the McLafferty rearrangement of radical cations and the Norrish II diradical rearrangement of aliphatic ketones. (iv) The charge-remote radical losses of MeȮ and ̇CO<inf>2</inf>Me occur from a 3-CO<inf>2</inf>Me substituent.