3.03 - Radical Reactivity by Computation and Experiment

M. L. Coote

doi:10.1016/B978-0-444-53349-4.00062-5

3.03 - Radical Reactivity by Computation and Experiment

M. L. Coote^*

^*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceeding › Chapter › peer-review

1 Citation (Scopus)

Abstract

This chapter discusses various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives, and explains the difference between stability and persistence. A large compilation of RSEs for carbon-centered radicals is presented and used to illustrate the principal structure–reactivity trends. Other key properties of the radicals and other reagents in free-radical polymerization reactions, including polarity, steric effects, and bond strengths, are also defined and discussed. Finally, it is shown how these factors combine to determine the kinetics and thermodynamics of the principal radical reactions in both conventional and controlled radical polymerization processes.

Original language	English
Title of host publication	Polymer Science
Subtitle of host publication	a Comprehensive Reference: Volume 1-10
Publisher	Elsevier
Pages	39-58
Number of pages	20
Volume	1-10
ISBN (Electronic)	9780080878621
DOIs	https://doi.org/10.1016/B978-0-444-53349-4.00062-5
Publication status	Published - 1 Jan 2012

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10.1016/B978-0-444-53349-4.00062-5

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title = "3.03 - Radical Reactivity by Computation and Experiment",

abstract = "This chapter discusses various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives, and explains the difference between stability and persistence. A large compilation of RSEs for carbon-centered radicals is presented and used to illustrate the principal structure–reactivity trends. Other key properties of the radicals and other reagents in free-radical polymerization reactions, including polarity, steric effects, and bond strengths, are also defined and discussed. Finally, it is shown how these factors combine to determine the kinetics and thermodynamics of the principal radical reactions in both conventional and controlled radical polymerization processes.",

keywords = "Atom transfer radical polymerization, Bond strength, Chain transfer processes, Curve-crossing model, Free-radical copolymerization, Free-radical polymerization, Halogen transfer, Hammett parameters, Hydrogen transfer, Kinetics, Linear free-energy relationships, Nitroxide-mediated polymerization, Propagation rate coefficients, Quantum chemistry, Radical addition, Radical reactivity, Radical stability, Radical stabilization energy, Reversible addition–fragmentation chain transfer (RAFT) polymerization, Substituent effects, Taft parameters, Thermodynamics",

author = "Coote, {M. L.}",

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doi = "10.1016/B978-0-444-53349-4.00062-5",

language = "English",

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T1 - 3.03 - Radical Reactivity by Computation and Experiment

AU - Coote, M. L.

PY - 2012/1/1

Y1 - 2012/1/1

N2 - This chapter discusses various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives, and explains the difference between stability and persistence. A large compilation of RSEs for carbon-centered radicals is presented and used to illustrate the principal structure–reactivity trends. Other key properties of the radicals and other reagents in free-radical polymerization reactions, including polarity, steric effects, and bond strengths, are also defined and discussed. Finally, it is shown how these factors combine to determine the kinetics and thermodynamics of the principal radical reactions in both conventional and controlled radical polymerization processes.

AB - This chapter discusses various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives, and explains the difference between stability and persistence. A large compilation of RSEs for carbon-centered radicals is presented and used to illustrate the principal structure–reactivity trends. Other key properties of the radicals and other reagents in free-radical polymerization reactions, including polarity, steric effects, and bond strengths, are also defined and discussed. Finally, it is shown how these factors combine to determine the kinetics and thermodynamics of the principal radical reactions in both conventional and controlled radical polymerization processes.

KW - Atom transfer radical polymerization

KW - Bond strength

KW - Chain transfer processes

KW - Curve-crossing model

KW - Free-radical copolymerization

KW - Free-radical polymerization

KW - Halogen transfer

KW - Hammett parameters

KW - Hydrogen transfer

KW - Kinetics

KW - Linear free-energy relationships

KW - Nitroxide-mediated polymerization

KW - Propagation rate coefficients

KW - Quantum chemistry

KW - Radical addition

KW - Radical reactivity

KW - Radical stability

KW - Radical stabilization energy

KW - Reversible addition–fragmentation chain transfer (RAFT) polymerization

KW - Substituent effects

KW - Taft parameters

KW - Thermodynamics

UR - http://www.scopus.com/inward/record.url?scp=84884933791&partnerID=8YFLogxK

U2 - 10.1016/B978-0-444-53349-4.00062-5

DO - 10.1016/B978-0-444-53349-4.00062-5

M3 - Chapter

VL - 1-10

SP - 39

EP - 58

BT - Polymer Science

PB - Elsevier

ER -

3.03 - Radical Reactivity by Computation and Experiment

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