Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 32, Pages 10971-10974Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201905325
Keywords
hydrogen atom transfer; iridium; oxo complexes; pincer complexes
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Funding
- Deutsche Forschungsgemeinschaft [389479699/RTG2455] Funding Source: Medline
- European Research Council [CoG 646747] Funding Source: Medline
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A terminal iridium oxo complex with an open-shell (S=1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide. Electronic structure examinations support large spin delocalization to the oxygen atom. Selected oxo transfer reactions indicate the ambiphilic reactivity of the iridium oxo moiety. Calorimetric and computational examinations of the HAT revealed a bond dissociation free energy for the IrO-H bond that is sufficient for hydrogen atom abstraction towards C-H bonds and small contributions from entropy and spin-orbit coupling to the HAT thermochemistry.
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