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Gauging Radical Stabilization with Carbenes.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Sep 12; Vol. 61 (37), pp. e202206390. Date of Electronic Publication: 2022 Aug 04. - Publication Year :
- 2022
-
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 π-donation to- and π-donation from the carbenes. This picture sheds a new perspective on NHC chemistry, where π-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.<br /> (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 61
- Issue :
- 37
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 35796423
- Full Text :
- https://doi.org/10.1002/anie.202206390