Multiple N-H and C-H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes

We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe-amine complexes 1-(NH), 1-(MeNH), and 1-(MeNH). Treatment of 1 or 1-(NH) to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical (ArO^•), under NH₃ resulted in catalytic H atom abstraction (HAA) and C-N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and ArOH. Exposing 1-(NH) to an excess of the trityl (CPh₃) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical (^TrArO^•), under NH₃ did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N-H and β C-H in the alkylamine congeners, 1-(MeNH) and 1-(MeNH), led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH)(CN), and imine complex, 1-(MeN═CH), respectively. Subsequent C-N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N-H and C-H HAA to generate these unsaturated products.