C-H Amination Mediated by Cobalt Organoazide Adducts and the Corresponding Cobalt Nitrenoid Intermediates

Treatment of (L-Ar)CoBr (L-Ar = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin) with a stoichiometric amount of 1-azido-4-(tertbutyl)benzene N-3(C(6)H(4)p-Bu-t) furnished the corresponding fourcoordinate organoazide-bound complex (L-Ar)CoBr(N-3(C6H4-p-Bu-t)). Spectroscopic and structural characterization of the complex indicated redox innocent ligation of the organoazide. Slow expulsion of dinitrogen (N-2) was observed at room temperature to afford a ligand functionalized product via a [3 + 2] annulation, which can be mediated by a high-valent nitrene intermediate such as a Co-III iminyl (L-Ar)CoBr(N-center dot(C6H4-p-Bu-t)) or Co-IV imido (L-Ar)CoBr(N(C6H4-p-Bu-t)) complex. The presence of the proposed intermediate and its viability as a nitrene group transfer reagent are supported by intermolecular C-H amination and aziridination reactivities. Unlike (L-Ar)CoBr(N-3(C6H4-p-Bu-t)), a series of alkyl azide-bound Co-II analogues expel N-2 only above 60 degrees C, affording paramagnetic intermediates that convert to the corresponding Co-imine complexes via alpha-H-atom abstraction. The corresponding N-2-released structures were observed via single-crystal-to-crystal transformation, suggesting formation of a Co-nitrenoid intermediate in solid-state. Alternatively, the alkyl azide- bound congeners supported by a more sterically accessible dipyrrinato scaffold L-tBu(L-tBu = 5-mesityl-(1,9-di-tert-butyl)dipyrrin) facilitate intramolecular 1,3-dipolar cycloaddition as well as C-H amination to furnish 1,2,3-dihydrotriazole and substituted pyrrolidine products, respectively. For the C-H amination, we observe that the temperature required for azide activation varies depending on the presence of weak C-H bonds, suggesting that the alkyl azide adducts serve as viable species for C-H amination when the C-H bonds are (1) proximal to the azide moiety and (2) sufficiently weak to be activated.