TY - JOUR
T1 - Selective Bond Cleavage in RAFT Agents Promoted by Low-Energy Electron Attachment
AU - Izadi, Farhad
AU - Arthur-Baidoo, Eugene
AU - Strover, Lisa T.
AU - Yu, Li-Juan
AU - Coote, Michelle L.
AU - Moad, Graeme
AU - Denifl, Stephan
PY - 2021/8/23
Y1 - 2021/8/23
N2 - Radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well-defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side-reactions and high spatio-temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low-energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C−S bond is induced upon low-energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (.CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.
AB - Radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well-defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side-reactions and high spatio-temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low-energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C−S bond is induced upon low-energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (.CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.
KW - dimethyl trithiocarbonate
KW - dissociative electron attachment
KW - low-energy electron
KW - radical polymerization
KW - RAFT agents
UR - http://www.scopus.com/inward/record.url?scp=85110960401&partnerID=8YFLogxK
UR - http://purl.org/au-research/grants/ARC/FL170100041
U2 - 10.1002/anie.202107480
DO - 10.1002/anie.202107480
M3 - Article
C2 - 34214239
AN - SCOPUS:85110960401
SN - 1433-7851
VL - 60
SP - 19128
EP - 19132
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 35
ER -