Enlightening the mechanism of copper mediated photoRDRP via high-resolution mass spectrometry
Frick, Elena, Anastasaki, Athina, Haddleton, David M., & Barner-Kowollik, Christopher (2015) Enlightening the mechanism of copper mediated photoRDRP via high-resolution mass spectrometry. Journal of the American Chemical Society, 137(21), pp. 6889-6896.
The initiation mechanism of photochemically mediated Cu-based reversible-deactivation radical polymerization (photoRDRP) was investigated using pulsed-laser polymerization (PLP) and high-resolution mass spectrometry. The variation of the catalyst composition and ESI-MS analysis of the resulting products provided information on how initiator, ligand, copper species, and monomer are interacting upon irradiation with UV light. A discussion of the results allows for a new postulation of the mechanism of photoRDRP and–for the first time–the unambiguous identification of the initiating species and their interactions within the reaction mixture. One pathway for radical generation proceeds via UV light-induced C–Br bond scission of the initiator, giving rise to propagating radicals. The generation of copper(I) species from copper(II) can occur via several pathways, including, among others, via reduction by free amine ligand in its excited as well as from its ground state via the irradiation with UV light. The amine ligand serves as a strong reducing agent and is likely the main participant in the generation of copper(I) species.
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|Item Type:||Journal Article|
|Divisions:||Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
|Copyright Owner:||Copyright 2015 American Chemical Society|
|Deposited On:||11 Aug 2016 23:23|
|Last Modified:||15 Aug 2016 01:47|
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