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-(NH3)(2), 1-MeNH2)(2), and 1-(Me2NH)(2). Treatment of 1 or 1-(NH3)(2) to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical ((ArO center dot)-Ar-tBu), 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)-Ar-tBu. Exposing 1-(NH3)(2) to an excess of the trityl (CPh3) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical ((ArO center dot)-Ar-Tr), 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 alpha N-H and beta C-H in the alkylamine congeners, 1-(MeNH2)(2) and 1-(Me2NH)(2), led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH2)(CN), and imine complex, 1-(MeN=CH2)(2), 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.