A convenient synthetic route for the preparation of nonsymmetric metallosalphen complexes

New nonsymmetric metallo(II)-salphen complexes 1-6 [salphen = N,N'-bis(salicylidene)-1,2-diaminobenzene, M = Zn, Ni] have been prepared in high yield by a templated, one-pot two-step procedure starting from substituted ortho-phenylenediamines, salicylaldehydes and metal acetates in MeOH under mild conditions. The procedure allows the introduction of functional groups in the bridging phenyl fragment, whereas the use of the substituted monoimine intermediates 7-10 results in complexes with two structurally different phenyl side groups with various functionalities (complexes 11-21) upon reaction with a second, different, salicylaldehyde reagent. A range of analytical tools confirmed the structures of these nonsymmetric salphen derivatives and the X-ray molecular structure of one of these nonsymmetric Zn-II-salphen complexes (i.e., 4) is also reported. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.