TY - CHAP
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 - 2006/9/7
Y1 - 2006/9/7
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.
UR - https://www.scopus.com/pages/publications/36949030001
U2 - 10.1021/bk-2006-0944.ch028
DO - 10.1021/bk-2006-0944.ch028
M3 - Chapter
AN - SCOPUS:36949030001
SN - 0841239916
SN - 9780841239913
VL - 944
T3 - ACS Symposium Series
SP - 406
EP - 420
BT - Controlled/Living Radical Polymerization
A2 - Matyjaszewsk, Krzysztof
PB - American Chemical Society (ACS)
CY - USA
ER -