The reactions between the tetradentate ligand o-HO- p-OMe–C 6H 3–C(Ph) N–(CH 2) 2–N C(Ph)–C 6H 3- o-OH- p-OMe ( 1) and the dichlorosilacycles [PhN-(CH 2) 2–NPh]SiCl 2 ( 2) and [Me 3SiN-( o-C 6H 4)-NSiMe 3]SiCl 2 ( 4) afforded the red colored complexes [ o-O- p-OMe–C 6H 3–C(Ph) N–(CH 2) 2–N C(Ph)–C 6H 3- o-O- p-OMe]Si{2N}, {2N} = [PhN–(CH 2) 2–NPh] ( 3), {2N} = [Me 3SiN-( o-C 6H 4)-NSiMe 3] ( 5) with hexacoordinate central silicon atom, respectively. The intense red color of these compounds originates from interligand charge transfer [(amide) → Si → (salen)]. Compound 3a, a cyclic dimer of 3 with tetracoordinate Si atoms, was isolated from the reaction mixture. It is colorless, thus demonstrating that the interligand charge transfer from the amide ligand to the salen-type ligand requires the connection of the imine N atoms to the Si atom and is not possible via an Si–O-connection to the salen-type ligand only. The reaction between ligand 1 and the dichlorosilacycle 7 [Ph 2MeSiN–(CH 2) 2–NSiMePh 2]SiCl 2 with bulky substituents at the amide N atoms gave rise to the monomeric salen-Si-compound 8 [ o-O- p-OMe–C 6H 3–C(Ph) N–(CH 2) 2–N C(Ph)–C 6H 3- o-O- p-OMe]Si[Ph 2MeSiN–(CH 2) 2–NSiMePh 2] bearing only tetracoordinate Si atoms. Compound 8 is also colorless. The formation of 8 from 1 and 7 was proven to occur via a hexacoordinate silicon complex 8a, which, however, could not be isolated so far.