Issue 21, 2007

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

Abstract

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 cm3 molecule−1 s−1): 18O2 (85 ± 4), NO (38.4 ± 0.4), I2 (50 ± 50), Br2 (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.

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

Article information

Article type
Paper
Submitted
20 7 2007
Accepted
10 9 2007
First published
19 9 2007

Org. Biomol. Chem., 2007,5, 3495-3503

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

D. G. Harman and S. J. Blanksby, Org. Biomol. Chem., 2007, 5, 3495 DOI: 10.1039/B711156H

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