Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach

Harman, D. G. & Blanksby, Stephen J. (2007) Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach. Organic & Biomolecular Chemistry, 5(21), pp. 3495-3503.

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The gas phase reactions of the bridgehead 3-carboxylato-1-adamantyl radical anion were observed with a series of neutral reagents using a modified electrospray ionisation linear ion trap mass spectrometer. This distonic radical anion was observed to undergo processes suggestive of radical reactivity including radical-radical combination reactions, substitution reactions and addition to carbon-carbon double bonds. The rate constants for reactions of the 3-carboxylato-1-adamantyl radical anion with the following reagents were measured ( in units 10(-12) cm(3) molecule(-1) s(-1)): O-18(2) ( 85 +/- 4), NO ( 38.4 +/- 0.4), I-2 ( 50 +/- 50), Br-2 ( 8 +/- 2), CH3SSCH3 ( 12 +/- 2), styrene ( 1.20 +/- 0.03), CHCl3 ( H abstraction 0.41 +/- 0.06, Cl abstraction 0.65 +/- 0.1), CDCl3 ( D abstraction 0.035 +/- 0.01, Cl abstraction 0.723 +/- 0.005), allyl bromide (Br abstraction 0.53 +/- 0.04, allylation 0.25 +/- 0.01). Collision rates were calculated and reaction efficiencies are also reported. This study represents the first quantitative measurement of the gas phase reactivity of a bridgehead radical and suggests that distonic radical anions are good models for the study of their elusive uncharged analogues.

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ID Code: 71661
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: quadrupole ion-trap, bridgehead radicals, mass-spectrometry, peptide, radicals, molecular-oxygen, butyl radicals, alkyl-halides, c-h, kinetics, cations
DOI: 10.1039/b711156h
ISSN: 1477-0539 (online) 1477-0520 (print)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2007 The Royal Society of Chemistry
Deposited On: 14 May 2014 22:38
Last Modified: 16 Jun 2014 10:08

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