Transition metal-bound nitrene complexes have received great attention as key intermediates for the direct incorporation of nitrene functionality into unreactive C−H bonds. Cobalt imido species have been relatively less explored in C-H amination transformations as the majority of these species feature low-spin electronic configurations, resulting in unreactive species. To overcome this limitation and generate a potent imido complex, our group has utilized the weak-field dipyrrin platform to synthesize paramagnetic Co(III) imido species. These Co(III) linear alkyl imido complexes are capable of intramolecular C-H amination to afford pyrrolidine products in a catalytic fashion. Further, we have found that the analogous pyridine-bound cobalt imido manifests enhanced reactivity toward C−H bond cleavage compared to the pyridine-free imido species. Ongoing efforts towards understanding the mechanistic details of C-H amination and the electronic nature of the pyridine-bound cobalt imido will be discussed herein.

Mechanistic studies of C-H amination processes mediated by dipyrrin-cobalt imidos

254th National Meeting (2017)

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