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 FeCl3, 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 I 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 I iron ion. This complex decomposes to produce a Fe(II) derivative which is further oxidized by MCPBA to generate a (1(.)Fe=O)(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). (C) 2004 Elsevier B.V. All rights reserved.