non-metal-mediated atom-transfer radical polymerization

initialism: NM-ATRP
https://doi.org/10.1351/goldbook.08926
Atom-transfer radical polymerization in which the deactivation of the radicals involves reversible atom transfer or reversible group transfer to a non-metallic reagent.
Notes:
  1. The activator is often incorrectly termed a catalyst. The term catalyst should only be used when referring to a species which is not changed as a consequence of reaction being considered.
  2. NM-ATRP may be referred to as ATRP.
  3. There are various forms of NM-ATRP that differ in details of the intimate mechanism, the reaction conditions and/or the reagents used. These include:
    1. RCTP (reversible chain-transfer-catalyzed polymerization). The group transferred (X) is often iodine and examples of the activator (R−X) are certain nitrogen, phosphorus, germanium, or tin compounds, which include germanium tetraiodide and 1-iodopyrrolidine-2,5-dione (traditional name is N-iodosuccinimide). Use of the term RCTP is deprecated. The mechanism is proposed to involve inner-sphere electron transfer atom-transfer radical polymerization (ISET-ATRP).
    2. RCMP (reversible-complexation-mediated radical polymerization) where the activator (typically an alkyl amine) reacts with an initiator (typically an alkyl iodide) by molecule-assisted homolysis to form the initiating species and an activator-complex.
    3. O-ATRP (organocatalyzed atom-transfer radical polymerization). A photochemically-mediated ATRP in which an organic photoredox catalyst such as perylene, a 5,10-diaryl-5,10-dihydrophenazine or a 10-aryl-10H-phenoxazine is used as the activator. The mechanism is proposed to involve outer-sphere electron transfer atom-transfer radical polymerization (OSET-ATRP).
Source:
PAC, 2022, 94, 1093. (Terminology for chain polymerization (IUPAC Recommendations 2021)) on page 1110 [Terms] [Paper]
Citation: 'non-metal-mediated atom-transfer radical polymerization' in IUPAC Compendium of Chemical Terminology, 5th ed. International Union of Pure and Applied Chemistry; 2025. Online version 5.0.0, 2025. https://doi.org/10.1351/goldbook.08926 RIS BibTex EndNote
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