Incorporation of thiolate donation using 2,2′-dithiodibenzaldehyde: synthesis of Ni, Fe, and Cu complexes. Crystal structures of [M(tsalen)] (tsalen=N,N′-ethylenebis(thiosalicylidene)imine); M=Cu, Ni) showing a tetrahedral distortion of Cu(tsalen)

Ethylenediamine complexes of Ni(II), Fe(III), and Cu(II) are combined with 2,2′-dithiodibenzaldehyde (DTDB) to form complexes with mixed N/S coordination spheres, demonstrating the generality of this synthetic methodology for metals other than Ni(II). Fe(en)33+ reacts with DTDB to give Fe(Haetsaln)2 + (Haetsaln=N-(2-aminoethyl)thiosalicylideneimine), stemming from the addition of a thiobenzaldehyde moiety from DTDB to one of the ethylenediamine N atoms. Ni(en)3 2+ and Cu(en)2 2+ react with DTDB to give Ni(tsalen) and Cu(tsalen) (tsalen=N,N′-ethylenebis(thiosalicylideneimine), stemming from the addition of a thiobenzaldehyde moiety to both ethylenediamine N atoms. A new crystal structure for Ni(tsalen) is reported, as well as the first crystal structure of Cu(tsalen), which shows a significant deviation from planarity in the N2S2 coordination sphere.