An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization

Elizabeth H. Krenske; Ekaterina I. Izgorodina; Michelle L. Coote

doi:10.1021/bk-2006-0944.ch028

An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization

Elizabeth H. Krenske, Ekaterina I. Izgorodina, Michelle L. Coote^*

^*Corresponding author for this work

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

27 Citations (Scopus)

Abstract

The effects of substituents on the addition-fragmentation reaction, P _n· + S=C(Z)SR → P_nSC·(Z)SR → P_nSC(Z)=S + R·, of the reversible addition fragmentation chain transfer (RAFT) process have been studied via high-level ab initio calculations. A number of simple isodesmic quantities are introduced in order to rank the stabilities of the RAFT agents and the RAFT-adduct radicals, together with the efficiency of addition-fragmentation and of the overall chain transfer process. The stabilities of me RAFT agents and RAFT-adduct radicals are mainly affected by the Z group, while the chain transfer efficiency depends mainly on the R group. The rankings can be used as a first-reference guide for selecting an R and Z group for a given polymerization.

Original language	English
Title of host publication	Controlled/Living Radical Polymerization from Synthesis to Materials
Publisher	American Chemical Society
Pages	406-420
Number of pages	15
ISBN (Print)	0841239916, 9780841239913
DOIs	https://doi.org/10.1021/bk-2006-0944.ch028
Publication status	Published - 2006

Publication series

Name	ACS Symposium Series
Volume	944
ISSN (Print)	0097-6156

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10.1021/bk-2006-0944.ch028

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@inproceedings{7557c62549da466c857b34b56860303f,

title = "An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization",

abstract = "The effects of substituents on the addition-fragmentation reaction, P n· + S=C(Z)SR → PnSC·(Z)SR → PnSC(Z)=S + R·, of the reversible addition fragmentation chain transfer (RAFT) process have been studied via high-level ab initio calculations. A number of simple isodesmic quantities are introduced in order to rank the stabilities of the RAFT agents and the RAFT-adduct radicals, together with the efficiency of addition-fragmentation and of the overall chain transfer process. The stabilities of me RAFT agents and RAFT-adduct radicals are mainly affected by the Z group, while the chain transfer efficiency depends mainly on the R group. The rankings can be used as a first-reference guide for selecting an R and Z group for a given polymerization.",

author = "Krenske, {Elizabeth H.} and Izgorodina, {Ekaterina I.} and Coote, {Michelle L.}",

year = "2006",

doi = "10.1021/bk-2006-0944.ch028",

language = "English",

isbn = "0841239916",

series = "ACS Symposium Series",

publisher = "American Chemical Society",

pages = "406--420",

booktitle = "Controlled/Living Radical Polymerization from Synthesis to Materials",

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}

An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization. / Krenske, Elizabeth H.; Izgorodina, Ekaterina I.; Coote, Michelle L.
Controlled/Living Radical Polymerization from Synthesis to Materials. American Chemical Society, 2006. p. 406-420 (ACS Symposium Series; Vol. 944).

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

TY - GEN

T1 - An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization

AU - Krenske, Elizabeth H.

AU - Izgorodina, Ekaterina I.

AU - Coote, Michelle L.

PY - 2006

Y1 - 2006

N2 - The effects of substituents on the addition-fragmentation reaction, P n· + S=C(Z)SR → PnSC·(Z)SR → PnSC(Z)=S + R·, of the reversible addition fragmentation chain transfer (RAFT) process have been studied via high-level ab initio calculations. A number of simple isodesmic quantities are introduced in order to rank the stabilities of the RAFT agents and the RAFT-adduct radicals, together with the efficiency of addition-fragmentation and of the overall chain transfer process. The stabilities of me RAFT agents and RAFT-adduct radicals are mainly affected by the Z group, while the chain transfer efficiency depends mainly on the R group. The rankings can be used as a first-reference guide for selecting an R and Z group for a given polymerization.

AB - The effects of substituents on the addition-fragmentation reaction, P n· + S=C(Z)SR → PnSC·(Z)SR → PnSC(Z)=S + R·, of the reversible addition fragmentation chain transfer (RAFT) process have been studied via high-level ab initio calculations. A number of simple isodesmic quantities are introduced in order to rank the stabilities of the RAFT agents and the RAFT-adduct radicals, together with the efficiency of addition-fragmentation and of the overall chain transfer process. The stabilities of me RAFT agents and RAFT-adduct radicals are mainly affected by the Z group, while the chain transfer efficiency depends mainly on the R group. The rankings can be used as a first-reference guide for selecting an R and Z group for a given polymerization.

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U2 - 10.1021/bk-2006-0944.ch028

DO - 10.1021/bk-2006-0944.ch028

M3 - Conference contribution

SN - 0841239916

SN - 9780841239913

T3 - ACS Symposium Series

SP - 406

EP - 420

BT - Controlled/Living Radical Polymerization from Synthesis to Materials

PB - American Chemical Society

ER -

An ab initio guide to structure-reactivity trends in reversible addition fragmentation chain transfer polymerization

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