Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide‐Mediated Synthesis Route

Reacting [NBu₄][OsNCl₄] with perfluorinated diols and alcohols in the presence of Ag₂O results in the formation of the corresponding Os(VI) nitrido complexes, [Os(N)(OR^F)₄]⁻ (OR^F = perfluorinated alcoholate), which contain perfluorinated alcoholate ligands. These complexes represent rare examples of osmium(VI) nitrido complexes with 4 O-donor ligands.

The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu₄][OsNCl₄] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C₆F₅OH) in the presence of Ag₂O to obtain the stable complexes [NBu₄][Os(N)(O₂C(CF₃)₂)₂] (1), [NBu₄][Os(N)(O₂C₂(CF₃)₄)₂] (2), [NBu₄][Os(N)(OC₆F₅)₄] (3), and [NBu₄][Os(N)(Cl)₂(O₂C(CF₃)₂)] (4) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four O-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes 1 and 4 extend the coordination chemistry of the otherwise underrepresented O₂C(CF₃)₂ ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds 1, 2, and 3 are analyzed.

Zum Volltext