Reactions of sulphur diimides with di- and tri-silanes: 15N and 29Si nuclear magnetic resonance study and the crystal structure of bis[tert-butyl(trichlorosilyl)amino]sulphane
Abstract
Sulphur diimides R1NSNR21a(R1= R2= But), 1b(R1= But, R2= Me3Si) and 1c(R1= R2= Me3Si) react with tetrachloro-1,2-dimethyldisilane 2, hexachlorodisilane 3 and octachlorotrisilane 6 by cleavage of the Si–Si bond to give the corresponding diaminosulphanes (4, 5, 7) in quantitative yield. In the case of 6 only one of the two Si–Si bonds is cleaved. The reaction between 1b and 6 affords two isomers in a ratio close to 1:1 which suggests the intermediacy of a cyclic adduct prior to the intramolecular redox process. The products have been characterized by 1H, 13C, 15N and 29Si NMR spectroscopy in solution as well as by 29Si cross polarization magic angle spinning NMR in the solid state. The crystal structure of (Cl3Si)ButNSNBut(SiCl3)5a(prepared from 1a and 3) has been determined: space group Pbcn(no. 60), with a= 2212.9(6), b= 1172.4(3), c= 2160.5(8) pm, and Z= 12.