The organotin(IV) chlorides R 2 SnCl 2 (R ¼ Ph and Me) react with a Schiff base (H 2 L), obtained from the condensation of 5-bromo-2-hydroxybenzaldehyde and ortho-aminophenol. Spectral properties of new complexes were investigated by infrared (IR), 1 H NMR, and 119 Sn NMR spectroscopy and show that in the two complexes H 2 L acts as a tridentate dianionic ligand and co-ordinates to the metal via two phenolic oxygens and one imine nitrogen. The 119 Sn NMR data are consistent with the presence of five-coordinate tin(IV) in solution. Thermal decomposition of the complexes has been studied by thermogravimetry and the activation energy has been determined by the Horowitz-Metzger method.