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Issue 21, 2007
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Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach

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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

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Publication details

The article was received on 20 Jul 2007, accepted on 10 Sep 2007 and first published on 19 Sep 2007


Article type: Paper
DOI: 10.1039/B711156H
Citation: Org. Biomol. Chem., 2007,5, 3495-3503
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    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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