The effect of remote substituents in free radical addition reactions: new evidence for the penultimate unit effect

Michelle L. Coote; Thomas P. Davis; Leo Radom

doi:10.1016/S0166-1280(98)00427-8

The effect of remote substituents in free radical addition reactions: new evidence for the penultimate unit effect

Michelle L. Coote, Thomas P. Davis, Leo Radom

Research output: Contribution to journal › Article › peer-review

34 Citations (Scopus)

Abstract

Ab initio molecular orbital calculations of the barrier for the addition of gamma-substituted propyl radicals to various alkenes indicate that substituents at the gamma position of a radical can significantly affect the barrier. This finding supports recent experimental evidence for an enthalpic penultimate unit effect in free-radical copolymerization. For the reactions studied in the present work, this penultimate unit effect is consistent with a significant polar contribution.

Original language	English
Pages (from-to)	91-96
Number of pages	6
Journal	Journal of Molecular Structure: THEOCHEM
Volume	461-462
DOIs	https://doi.org/10.1016/S0166-1280(98)00427-8
Publication status	Published - 2 Apr 1999
Externally published	Yes

Keywords

Addition
Free radical
Gamma substituent effect
Penultimate unit effect
Polymerization

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keywords = "Addition, Free radical, Gamma substituent effect, Penultimate unit effect, Polymerization",

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AU - Radom, Leo

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N2 - Ab initio molecular orbital calculations of the barrier for the addition of gamma-substituted propyl radicals to various alkenes indicate that substituents at the gamma position of a radical can significantly affect the barrier. This finding supports recent experimental evidence for an enthalpic penultimate unit effect in free-radical copolymerization. For the reactions studied in the present work, this penultimate unit effect is consistent with a significant polar contribution.

AB - Ab initio molecular orbital calculations of the barrier for the addition of gamma-substituted propyl radicals to various alkenes indicate that substituents at the gamma position of a radical can significantly affect the barrier. This finding supports recent experimental evidence for an enthalpic penultimate unit effect in free-radical copolymerization. For the reactions studied in the present work, this penultimate unit effect is consistent with a significant polar contribution.

KW - Addition

KW - Free radical

KW - Gamma substituent effect

KW - Penultimate unit effect

KW - Polymerization

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DO - 10.1016/S0166-1280(98)00427-8

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JF - Journal of Molecular Structure: THEOCHEM

ER -

The effect of remote substituents in free radical addition reactions: new evidence for the penultimate unit effect

Abstract

Keywords

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