ic0c00654_si_001.pdf (1.1 MB)
Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π‑Acceptor Metallaligand in a Heterobimetallic OsVIN–PtII Complex
journal contribution
posted on 2020-03-31, 12:04 authored by Anders Reinholdt, Abraham B. Alemayehu, Kevin J. Gagnon, Jesper Bendix, Abhik GhoshPresented 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 OsVINPtII 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.