Gauging Radical Stabilization with Carbenes
Breitwieser K, Bahmann H, Weiss R, Munz D (2022)
Publication Type: Journal article
Publication year: 2022
Journal
Abstract
Carbenes, including N-heterocyclic carbene (NHC) ligands, are used extensively to stabilize open-shell transition metal complexes and organic radicals. Yet, it remains unknown, which carbene stabilizes a radical well and, thus, how to design radical-stabilizing C-donor ligands. With the large variety of C-donor ligands experimentally investigated and their electronic properties established, we report herein their radical-stabilizing effect. We show that radical stabilization can be understood by a captodative frontier orbital description involving pi-donation to- and pi-donation from the carbenes. This picture sheds a new perspective on NHC chemistry, where pi-donor effects usually are assumed to be negligible. Further, it allows for the intuitive prediction of the thermodynamic stability of covalent radicals of main group- and transition metal carbene complexes, and the quantification of redox non-innocence.
Involved external institutions
Germany (DE)How to cite
APA:
Breitwieser, K., Bahmann, H., Weiss, R., & Munz, D. (2022). Gauging Radical Stabilization with Carbenes. Angewandte Chemie International Edition. https://dx.doi.org/10.1002/anie.202206390
MLA:
Breitwieser, Kevin, et al. "Gauging Radical Stabilization with Carbenes." Angewandte Chemie International Edition (2022).
BibTeX: Download