Diimines obtained from 3,3‘-diaminobenzidine and tert-butyl-substituted salicylaldehydes in MeOH can be readily isolatedin 60−90% yield and were obtained as a mixture ofgeometrical isomers. Two distinct diimine intermediates (4and 5) with a higher molecular symmetry as related to theother isomeric diimine products were both isolated bycrystallization of which 5 was subsequently used to demonstrate that nonsymmetrical bis-salphen complexes withdifferent functional groups and metal centers can be assembled via a three-component one-pot procedure.