Low temperature selective transformation of alkanes to useful products continues to be an important challenge in chemistry and industry. mu-Nitrido diiron phthalocyanines in combination with H2O2 have been recently identified as powerful oxidation catalysts for these challenging reactions due to the formation of ultra-high valent diiron oxo species PcFe(IV)mu NFe(IV)=O(Pc+center dot). This very strong two-electron oxidizing species is generated from peroxo complex PcFe(IV)mu NFe(III)-O-O-R(Pc) (R=H in the case of H2O2) via heterolytic O-O bond cleavage. Therein we show that the evolution of the peroxo diiron complex depends on the peroxide structure. Using tBuOOH we have demonstrated the formation of an one-electron oxidizing PcFe(IV)mu NFe(IV)=O(Pc) and (BuO center dot)-Bu-t radical via homolytic O-O cleavage of the peroxocomplex. The reactivity of the-nitrido diiron tetra-t-butylphthalocyanine - (BuOOH)-Bu-t catalytic system was investigated in the oxidation of different C H bonds in alkanes, olefins, aromatic and alkylaromatic compounds. The main products of cyclohexane oxidation were cyclohexanone and cyclohexanol whereas bicyclohexyl was formed in minor amounts even in the presence of O-2 and (BuOOH)-Bu-t. Under optimal conditions, the turnover numbers of almost 5300 have been achieved. (C) 2016 Elsevier B.V. All rights reserved.