Ketimines (K1, K2) and aldimines (A1, A2, and A3) were prepared from unsubstituted acetophenone and/or benzaldehyde and primary amines ( i -PrNH 2 , i -BuNH 2 and t -BuNH 2 ). These imines were reacted with Zeise’s salt (potassium ethenetrichloroplatinate(II)) to produce the respective complexes, namely, PtK1 , PtK2 , PtA1 , PtA2 , and PtA3 . 1 H, 13 C, and 195 Pt-chemical shifts of the ligands and their complexes were studied to investigate the nature and mode of isomerization around C N bond. The aldimines and their complexes were obtained as a single isomer. On the other hand, the ketimines and their complexes were obtained as a mixture of E / Z -isomers. It was found that the aldimine- and ketimine-platinum complexes undergo slow E / Z -isomerization in solution as evidenced from NMR spectra.