C–H Bond Activation via Photolysis of a Mn Nitride Ligand Radical Complex
We report the thermal and photoactivation of a solution-stable Mn nitride ligand radical complex <b>[Mn</b><sup><b>V</b></sup><b>(Sal</b><sup><b>NMe2•</b></sup><b>)N]</b><sup><b>+</b></sup>, which facilitates N-N bond homocoupling to generate N<sub>2</sub>, a reaction commonly observed in Mn<sup>VI</sup> nitrides. Theoretical calculations suggest that the nitride is ambiphilic, facilitating the N-N bond formation. Notably, photoactivation of the Mn<sup>V</sup> ligand radical at room temperature enables rapid C-H bond activation, leading to the formation of C-N insertion products, excluding dihydroanthracene where a desaturation product is observed. This study presents a rare example of photochemically driven intermolecular N atom transfer to a C-H bond mediated by a first-row Mn terminal nitride complex, made possible by the unique stability and turn-on reactivity of the oxidized ligand radical electronic structure.
Authors
- Fabrice Thomas (ORCID: https://orcid.org/0000-0002-6977-5192)
- Tim Storr (ORCID: https://orcid.org/0000-0002-3163-6218)
- Loren G. Kaake (ORCID: https://orcid.org/0000-0002-2085-8501)
- Samyadeb Mahato (ORCID: https://orcid.org/0009-0005-9153-3244)
- Omar Castro-Sandoval (ORCID: https://orcid.org/0000-0002-2846-5462)
- Ryan M. Clarke (ORCID: https://orcid.org/0000-0003-3356-071X)
- Saeid Kamal (ORCID: https://orcid.org/0000-0003-2758-4459)
- Olivier Jarjayes (ORCID: https://orcid.org/0000-0001-6223-9429)
- Vanessa Cheung
Institutions
- University of British Columbia (CA)
- Simon Fraser University (CA)
- Advanced Imaging Research (United States) (US)
- Université Grenoble Alpes (FR)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-09-03
- DOI
- https://doi.org/10.1021/jacs.5c10538
- Primary Topic
- Catalytic C–H Functionalization Methods
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Mitacs
- Natural Sciences and Engineering Research Council of Canada