Synthesis and structural characterization of neutral hexacoordinate silicon(IV) complexes containing salophen and thiocyanato-N ligands

摘要

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.