Journal
INORGANIC CHEMISTRY
Volume 59, Issue 8, Pages 5276-5280Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c00654
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Funding
- Research Council of Norway [262229]
- Carlsberg Foundation [CF18-0613]
- Independent Research Fund Denmark [9036-00015B]
- Advanced Light Source, a DOE Office of Science User Facility [DE-AC02-05CH11231]
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Presented herein is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. Elemental chlorine perchlorinates the beta-positions of the triarylcorrole but leaves the OsN unit untouched. The OsN unit is also unaffected by a variety of other electrophilic and nucleophilic reagents. Upon photolysis, however, the anion of Zeise's salt associates with the nitrido ligand to generate an Os-VI n-Pt-II complex. The very short OsN-Pt linkage [1.895(9)-1.917(8) angstrom] and the downfield Pt-195 NMR resonance (-2702 ppm) suggest that the OsN corrole acts as a pi-accepting ligand toward the Pt(II) center. This finding represents a rare example of the successful photochemical activation of a metal-ligand multiple bond that is too kinetically inert to exhibit any appreciable reactivity under thermal conditions.
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