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Two tetrakis(sulfurdiimido)silanes [Si(NSNR) 4  (R =  t Bu 1a, SiMe 3  1b)], two germanes [Ge(NSNR) 4  (R =  t Bu 2a, SiMe 3  2b)] and one stannane [Sn(NSN t Bu) 4 Sn 3a] were prepared and characterised by  1 H,  13 C,  15 N,  29 Si and  119 Sn NMR spectroscopy in solution, and 3a was also studied in the solid state by  119 Sn CP/MAS NMR. Whereas 1a,b and 2a,b are monomeric in solution, the  119 Sn NMR data suggest that 3a is associated both in solution and in the solid state, and that the tin atoms are hexa-coordinated. The attempted stepwise synthesis of 1a by using one, two, three or four equivalents of K[(NSN) t Bu] led to mixtures of 1a with Cl 3 Si(NSN t Bu) 4a, Cl 2 Si(NSN t Bu) 2  5a, and ClSi(NSN t Bu) 3  6a. Only one sulfurdiimido ligand of the silane 1a reacted with hexachlorodisilane by oxidative addition and cleavage of the Si-Si bond to give the new heterobicyclic derivative 7a which is held together by two different coordinative N-Si bonds.

Tetrakis(sulfurdiimido)silane, -germane and -stannane