Solid-state structure of sulfur bis(trimethylsilylimide), S(NSiMe3)2, and multinuclear magnetic resonance studies of some sulfur bis(silylimides) in solution

Abstract

In the solid state sulfur bis(trimethylsilylimide)1 has been shown to adopt the E/Z configuration by single-crystal X-ray diffraction (space group P, triclinic). In solution sulfur bis(silylimides) R(NSN)R′[R = R′= SiMe₃1 or Si₂Me₅2; R = SiMe₃, R′= Si₂Me₅3 or SiMe₂SiMe₂(NSN)SiMe₃4] are fluxional at room temperature. Comparison of the ¹H, ¹³C, ²⁹Si and, in particular, ¹⁵N NMR data indicates that 1 and 2 undergo rapid E/Z⇌Z/E isomerization even at 173 K, whereas in the case of 3 and 4 this process is slowed at low temperature and the E/Z configuration prevails with the SiMe₃ group in the E position.