A series of mononuclear Mn II and Mn IV complexes of general formulae [MnL 2 (NCS) 2 ] (1a-1d) and [Mn(L¢) 2 (NCS) 2 ] (2a-2c) have been prepared where L are Schiff bases obtained by the condensation of pyridine-2-aldehyde with para-alkyl-substituted aniline, and L¢ are the corresponding amide ligands. The room temperature magnetic susceptibility data of (1a-1d) indicate that Mn II is in a high spin state. The cyclic voltammograms of (1a-1d) exhibit a one-electron quasi-reversible Mn II fiMn III oxidation. A linear correlation has been found when E 0 [Mn III /Mn II ] is plotted against Hammett r p parameters. X-ray crystallographic data of (1b) shows that the central Mn II ion adopts a distorted octahedral geometry with six different MnAN distances. Upon oxidation of Mn II complexes (1b-1d) by H 2 O 2 , the corresponding Mn IV complexes (2a-2c) were obtained, and the Schiff base ligands were oxidized to the corresponding amides. The lowest energy LMCT bands of these Mn IV complexes correlate linearly with Hammett r p parameters. The redox behavior of the Mn IV complexes has been investigated by cyclic voltammetry. E.p.r. spectra of the Mn II and Mn IV complexes are also reported.