Abstract
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 β-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 OsVI≡N—PtII complex. The very short OsN–Pt linkage [1.895(9)–1.917(8) Å] and the downfield 195Pt NMR resonance (−2702 ppm) suggest that the OsN corrole acts as a π-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.
Highlights
Presented is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability
Corrole acts as a π-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
OsVIN corroles are surprisingly inert toward Corresponding Authors both nucleophilic and electrophilic reagents
Summary
Presented is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. 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. A preliminary examination of the reactivity of the OsVIN corroles with both nucleophilic (PPh3) and electrophilic reagents (MeI, I2) failed to yield the expected nitride-derived products.
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