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Selective Bond Cleavage in RAFT Agents Promoted by Low‐Energy Electron Attachment
Author(s) -
Izadi Farhad,
ArthurBaidoo Eugene,
Strover Lisa T.,
Yu LiJuan,
Coote Michelle L.,
Moad Graeme,
Denifl Stephan
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202107480
Subject(s) - raft , chemistry , reversible addition−fragmentation chain transfer polymerization , polymerization , chain transfer , electron transfer , homolysis , photochemistry , bond cleavage , radical , radical polymerization , dissociation (chemistry) , fragmentation (computing) , polymer , chemical physics , organic chemistry , computer science , catalysis , operating system
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 ( . CH 3 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.