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^*

^*Corresponding author for this work

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

36 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

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10.1016/S0166-1280(98)00427-8

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title = "The effect of remote substituents in free radical addition reactions: New evidence for the penultimate unit effect",

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.",

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

author = "Coote, \{Michelle L.\} and Davis, \{Thomas P.\} and Leo Radom",

year = "1999",

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T1 - The effect of remote substituents in free radical addition reactions

T2 - New evidence for the penultimate unit effect

AU - Coote, Michelle L.

AU - Davis, Thomas P.

AU - Radom, Leo

PY - 1999/4/2

Y1 - 1999/4/2

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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U2 - 10.1016/S0166-1280(98)00427-8

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

M3 - Article

SN - 0166-1280

VL - 461-462

SP - 91

EP - 96

JO - Journal of Molecular Structure: THEOCHEM

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

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