title: Should dithiophosphinate esters function as RAFT agents?
abstract: [graph: see text] High-level ab initio calculations indicate that *CH3 addition to the sulfur center of S=P(Z)(Z')SCH3 (Z,Z' = CH3, CN, OCH3, Ph) is considerably less exothermic than addition to the corresponding RAFT agents, S=C(Z)SCH3. This suggests that dithiophosphinate esters may have only limited use in controlling free-radical polymerization, but should make excellent radical chain carriers in organic synthesis. The results cast doubt on the notion that phosphoranyl radicals are more "intrinsically" stabilized than carbon-centered radicals.
authors.affiliation: ARC Centre of Excellence in Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia.
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Hodgson
authors.forename: Katy A
authors.initials: KA
authors.lastname: Green
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Coote