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Carbonyl group stabilization of radicals: Solvent effects on azoalkane decomposition

✍ Scribed by Al Luedtke; Kim Meng; Jack W. Timberlake

Publisher
Elsevier Science
Year
1987
Tongue
French
Weight
235 KB
Volume
28
Category
Article
ISSN
0040-4039

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✦ Synopsis

The synthesis and rates of decomposition of bis(l,l-dimethyl-2-oxopropyl) diazene (2~) are described.

A series of substituted azoalkanes is compared to four other systems measuring radical substituent effects.

These correlations and a solvent polarity study indicate the lack of polar contributions in azo decompositions. Carbonyl group stabilization of carbanions is the result of both favorable inductive and resonance effects. Carbocations, on the other hand, show slight stabilization in some cases and destablization in others. This appears to be the result of unfavorable electron withdrawing inductive effects and stabilizing resonance effects operating in opposite directions to different extents.l-3 The effect on radicals is of interest as they can be regarded as one electron oxidants of anions or one electron reductants of cations. As such, it is not easy, a priori, to predict what overall influence carbonyl functionalization might have.

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