A series of cobalt-arylnitrenoid complexes with the formula Co(NAr)(RPNP) (RPNP= anion of 2,5-bis((dialkylphosphino)methyl)pyrrole, R= Cy, tBu) were prepared by reaction of the corresponding Co(I)-RPNP complex with aryl azides. Crystallographic analysis reveals that the dominant resonance form of the resulting species can be best described as a dearomatized aryl ketimide p-radical bound to a low-spin Co(II) center. Unlike other metal-nitrene complexes featuring 3dmetals, these complexes show remarkable stability towards benzylic C-H bonds and olefins; this disparity in reactivity is explained through examination of the complex’s electronic structure and reactivity with small molecules.

Preparation and reactivity of cobalt-nitrenoid species supported by anionic PNP pincer ligands

2019 Spring National Meeting

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