Ocaña, Ivan, Griffin, Neil, Hodges, George et al. (2 more authors) (2025) Molecule-Induced Radical Formation (MIRF) Reaction of Et2BOOEt with Et3B is Key to the Et3B/O2 Radical Initiation. Chemistry - A European Journal. e02339. ISSN: 0947-6539
Abstract
Open-to-air triethylborane (Et3B) is a well-known room-temperature initiator of free radical reactions. Current consensus is that the initiating species in this system are ethyl radicals formed in the triethylborane autoxidation cycle, although some early studies suggested that reactions of the oxidation products can also contribute to the initiation. We report a quantitative mechanistic study which demonstrates that most ethyl radicals in the triethylborane initiator system are not formed in the autoxidation cycle but instead are generated by a Molecule-Induced Radical Formation (MIRF) reaction between triethylborane and its main oxidation product, ethylperoxyborane Et2BOOEt (secondary initiation). A simplified kinetic model allowed us to predict optimal conditions for the initiation, and propose the MIRF reaction as an alternative, homogeneous initiator system. The high efficiency of this initiator has been demonstrated in several model radical reactions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2025 Wiley-VCH GmbH. This is an author-produced version of the published paper. Uploaded in accordance with the University’s Research Publications and Open Access policy. |
Keywords: | borane autoxidation,molecule-induced radical formation,peroxyborane,radical initiators,reaction mechanism |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Date Deposited: | 30 Sep 2025 13:10 |
Last Modified: | 30 Sep 2025 13:10 |
Published Version: | https://doi.org/10.1002/chem.202502339 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1002/chem.202502339 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:232397 |