Transition metal nitrene complexes have received great attention as viable N-group transfer reagents into unreactive C−H bonds. Towards this end, organoazides (N3R) represent one of the most common nitrene sources (NR) for generation of such complexes upon rapid expulsion of dinitrogen (N2). While many metal nitrene compounds have been synthesized using this strategy, the corresponding metal-organoazide adduct complexes are relatively rare. Despite the transient nature of such metal bound organoazide species, our group has successfully isolated a series of dipyrrinato cobalt(II) organoazide complexes. The binding mode of the azide moiety towards the metal center is best described as a redox-neutral interaction as confirmed by by single crystal X-ray diffraction, solution IR spectroscopy, and solid-state EPR spectroscopy. Notably, these cobalt-organoazide adducts manifest both intra- and intermolecular C-H amination reactivity upon loss of N2, suggesting the potential involvement of a highly reactive intermediate such as a cobalt iminyl complex. The spectroscopic characterizations of these unusual cobalt-organoazide adduct complexes along with their nitrene group transfer reactivity will be discussed herein.

Synthesis of cobalt-organoazide adduct complexes and their C−H amination reactivity

256th National Meeting (2018)

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