From the reactions of SnCl4 with organotin(IV) chlorides (RSnCl3, R2SnCl2 and R3SnCl, where R = Bu, Me and Ph) with N-(2-hydroxybenzaldehyde)-1-amino-2-phenyleneimine, N-(2-hydroxyl-1-naphthaldehyde)-1-amino-2-phenyleneimine, N,N′-bis(2-hydroxybenzaldehyde)-1,2-phenylenediimine and N,N′-bis(2-hydroxy-1-naphthaldehyde)-1,2-phenylenediimine a series of complexes have been synthesized and characterized, respectively, by microanalytical, IR, and 1H NMR spectroscopic methods. The Ph2SnCl2 reacted with N-(2-hydroxy-1-naphthaldehyde)-1-amino-2-phenyleneimine giving Ph2Sn(NAPPDI) [where NAPPDI = deprotonated N,N′-bis(2-hydroxy-1-naphthaldehyde)-1,2-phenylenediimine], wherein the former Schiff base exhibit a facile intramolecular CN bond cleavage and intermolecular CN bond formation.