Visible light activation of C–Cl and C–F bonds in persistent organic pollutants using cerium( <scp>iii</scp> ) triamidoamine complex
Procedures for activating and degrading compounds containing carbon-halogen bonds are highly sought after due to the environmental persistence and potential hazards of such compounds. Such activations are challenging because of the high stability of these bonds, particularly those with C-F bonds. Here, we report on the activation of carbon-halogen bonds, including C-F bonds, by the cerium(iii)-triamidoamine complex Ce<sup>III</sup>TREN<sup>TIPS</sup> (1, TREN<sup>TIPS</sup> = tris-(2-(tri-iso-propylsilylamidoethyl)amine)). Under light irradiation, 1 reaches a strongly negative excited state redox potential, and our measurements enable it to be estimated as -3.2 V relative to Cp<sub>2</sub>Fe<sup>0/+</sup>. Hence, the photo-reactivity of 1 with carbon-halogen bonds has been established with numerous examples, including Persistent Organic Pollutants (POPs) and fluorinated compounds. The photoactivation of POPs is rapid, but the photoactive nature of the cerium(iv) products precludes complete conversion. This study provides insight into the activation of POPs that may benefit the future design of photodegradation approaches for these highly problematic compounds.
Authors
- Cédric Tard (ORCID: https://orcid.org/0000-0002-1515-1915)
- Grégory Nocton (ORCID: https://orcid.org/0000-0003-0599-1176)
- Ashley J. Wooles (ORCID: https://orcid.org/0000-0001-7411-9627)
- Matthew Gregson
- Adrien Combourieu (ORCID: https://orcid.org/0000-0002-2446-7284)
- Grégory Danoun (ORCID: https://orcid.org/0000-0003-2646-0091)
- Ákos Bányász (ORCID: https://orcid.org/0000-0002-2412-3019)
- Stephen T. Liddle (ORCID: https://orcid.org/0000-0001-9911-8778)
- Olivier Maury (ORCID: https://orcid.org/0000-0002-4639-643X)
- Nicolas Casaretto (ORCID: https://orcid.org/0000-0003-0636-983X)
- Stella Christodoulou
- Bich Tuyen Phung
- Laurent Maron (ORCID: https://orcid.org/0000-0003-2653-8557)
- Eachann Assendjee (ORCID: https://orcid.org/0009-0007-8104-2358)
Institutions
- École Normale Supérieure de Lyon (FR)
- Centre National de la Recherche Scientifique (FR)
- Université Toulouse III - Paul Sabatier (FR)
- École Polytechnique (FR)
- Université de Lyon (FR)
- University of Manchester (GB)
- Laboratoire de Physique de l'ENS de Lyon (FR)
- Laboratoire de Chimie Moléculaire (FR)
- Laboratoire de Chimie (FR)
- Laboratoire de Physique et Chimie des Nano-Objets (FR)
Publication Details
- Journal
- Chemical Science
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5sc03626g
- Citations
- 2
- Primary Topic
- Chemical Synthesis and Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Alexander von Humboldt-Stiftung
- Institut Polytechnique de Paris
- University of Manchester
- Agence Nationale de la Recherche
- Centre National de la Recherche Scientifique
- Institut Universitaire de France
- Engineering and Physical Sciences Research Council