DOI: 10.1002/ange.202316729 ISSN: 0044-8249
C–H Bond Activation by Iridium(III) and Iridium(IV) Oxo Complexes
Martijn Alexander Tepaske, Arnd Fitterer, Henrdik Verplancke, Daniel Delony, Marc C. Neben, Bas de Bruin, Max C. Holthausen, Sven Schneider- General Medicine
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.