Abstract Tetradentate amine N, N′-bis(2-pyridylmethylene)-1,4-diaminodiphenyl ether (compound 1) dramatically accelerates the oxidation of alkanes with MCPBA in acetonitrile catalyzed by FeCl 3, whereas N,N′-bis(2-pyrrolidinmethylene)-1,4-diaminodiphenyl ether ( 2) does not affect the reaction. The selectivity of the reaction in the presence of 1 is noticeably higher than that in its absence. On the basis of the kinetic study and selectivity parameters a mechanism has been proposed which includes the formation of a complex between a molecule of MCPBA and coordinated to ligand 1 iron ion. This complex decomposes to produce a Fe(II) derivative which is further oxidized by MCPBA to generate a ( 1·FeO) 4+ species reacting with both alkane and acetonitrile. Finally, alkyl hydroperoxide is formed which partially decomposes to produce more stable corresponding alcohol and ketone (aldehyde).