C-H Bond Activation by Iridium(III) and Iridium(IV) Oxo Complexes.
C-H activation
Quantum chemistry
oxo complexes
tunneling
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
20 Dec 2023
20 Dec 2023
Historique:
revised:
18
12
2023
received:
03
11
2023
accepted:
19
12
2023
medline:
20
12
2023
pubmed:
20
12
2023
entrez:
20
12
2023
Statut:
aheadofprint
Résumé
Oxidation of an iridium(III) oxo precursor enabled the structural, spectroscopic, and quantum-chemical characterization of the first well-defined iridium(IV) oxo complex. Side-by-side examination of the proton-coupled electron transfer thermochemistry revealed similar driving forces for the isostructural oxo complexes in two redox states due to compensating contributions from H+ and e- transfer. However, C-H activation of dihydroanthracene revealed significant hydrogen tunnelling for the distinctly more basic iridium(III) oxo complex. Our findings complement the growing body of data that relate tunnelling to ground state properties as predictors for the selectivity of C-H bond activation.
Identifiants
pubmed: 38116899
doi: 10.1002/anie.202316729
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202316729Informations de copyright
© 2023 Wiley-VCH GmbH.