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

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 ?-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) Å] and the downfield ¹⁹⁵Pt NMR resonance (-2702 ppm) suggest that the OsN corrole acts as a ?-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.

SUBMITTER: Reinholdt A 

PROVIDER: S-EPMC7311052 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature