Term: non-metal-mediated atom-transfer radical polymerization
https://doi.org/10.1351/goldbook.08926

Definition:
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: RCTP (reversible chain-transfer-catalyzed polymerization). The group transferred (\(\ce{X}\)) is often iodine and examples of the activator (\(\ce{R-X}\)) 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).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.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).

Related Term: outer-sphere electron transfer atom-transfer radical polymerization (oset-atrp) (http://doi.org/10.1351/goldbook.08927).
Related Term: inner-sphere electron transfer atom-transfer radical polymerization (http://doi.org/10.1351/goldbook.08925).
Related Term: initiating species (http://doi.org/10.1351/goldbook.08959).
Related Term: atrp (http://doi.org/10.1351/goldbook.08924).
Related Term: atrp (http://doi.org/10.1351/goldbook.08924).
Related Term: atom-transfer radical polymerization (http://doi.org/10.1351/goldbook.08924).
Related Term: deactivation (http://doi.org/10.1351/goldbook.08949).

Source: PAC, 2022, 94, 1093. 'Terminology for chain polymerization (IUPAC Recommendations 2021)' on page 1110 (https://doi.org/10.1515/pac-2020-1211)

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

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