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|Title:||The search for charge-remote reactions of even-electron anions derived from 1,3-disubstituted adamantanes in the gas phase. Retro Diels-Alder and Norrish II processes|
|Citation:||Rapid Communications in Mass Spectrometry, 2001; 15(15):1304-1308|
|Publisher:||John Wiley & Sons Ltd|
|Suresh Dua, John H. Bowie|
|Abstract:||The collision induced decompositions of 3-substituted adamantane carboxylate anions have been studied with a view to uncovering charge-remote fragmentations of the 3-substituent. The 3-substituent is chosen so that it cannot approach the anion site, and so any fragmentations of that substituent should proceed independently of the charged centre, viz. charge-remote reactions. The following systems have been studied (i) the 3-cyclohexenyl system shows no charge-remote retro Diels-Alder fragmentation (DeltaH = +157 kJ mol(-1)), instead, charge-remote loss of the cyclohexenyl radical is noted, (ii) the 3-isobutyl ketone system shows no Norrish II cleavage (loss of C(3)H(6), DeltaH = +18 kJ mol(-1)), instead, the competitive losses of CO(2) from the charged carboxyl centre, together with charge-remote radical loss of the 3-substituent are observed, and (iii) the corresponding 3-isopropyl ester does show the "Norrish II" loss of C(3)H(6), together with competitive losses of CO(2) and the 3-substituent. It is concluded for cases (ii) and (iii), that an adamantane carboxylate anion system with a carbonyl group directly attached at the 3-position is not a suitable model system for studying charge-remote reactions.|
|Description:||The definitive version may be found at www.wiley.com|
|Appears in Collections:||Chemistry publications|
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