Abstract The reaction of the H 2 salophen ligand, 2,2′-((1E,1′E)-(1,2-phenylenebis(azanylylidene))bis (methanylylidene))diphenol, with one molar equivalent of Si(NCS) 4 , MeSi(NCS) 3 ( 13 ), or HMeSi(NCS) 2 afforded neutral hexacoordinate silicon complexes, which have an-NCS bi-functionality (complex 1 ) and mono-functionality (complex 14 ). The reaction of Si(NCS) 4 with the H 2 salophen-type ligand1,1′-((1E,1′E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene)) bis(naphthalen-2-ol) (H 2 Noph), afforded the hexacoordinate silicon complex 15 , which has an-NCS bi-functionality. Single-crystal X-ray structural and elemental analyses were used to characterize and confirm the structure of the starting material 13 and complexes 1 , 14 , and 15 . The complexes were characterized in solution by 1 H, 13 C, and silicon-29 nuclear magnetic resonance ( 29 Si NMR) and in the solid state by 29 Si cross-polarization/magic angle spinning (CP/MAS) NMR. Because of the poor solubility of complex 1 , it was only possible to characterize it in the solid state by 13 C and 29 Si CP/MAS NMR and in solution by 1 H NMR.