Synthesis and characterization of silicon(IV) complexes with tetrasulphur tetraimide (S4N4H4)

Abstract

A new complex of S₄N₄H₄ with SiCl₄ has been synthesized by refluxing SiCl₄ and S₄N₄H₄ in equimolar ratio in benzene. The complex has the composition [S₄N₄H₄· SiCl₄]₃. When it is kept at 373 K and 1.775 x 10⁵ dyn/cm² in an autoclave, a new species entirely different in structure and properties is obtained which has the composition [S₄N₄H₄· SiCl₄]₁₁. From their quantitative estimations, IR, electronic spectral and XRD diffractometeric analysis, it is concluded that the complex [S₄N₄H₄· SiCl₄]₃ is N-coordinated trimer, while the complex [S₄N₄H₄· SiCl₄]₁₁is a polymeric complex having covalently linked Si(IV) with antipodal N atoms of S₄N₄H₄ and hexagonal unit cells. Both polymers are semiconductors.