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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 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 Os≡N-Pt complex. The very short OsN-Pt linkage [1.895(9)-1.917(8) Å] and the downfield Pt 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.

inorganic chemistry

Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os<sup>VI</sup>N–Pt<sup>II</sup> Complex

Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic OsVIN–PtII Complex

Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os^VIN–Pt^II Complex