Abstract
Reactions of metallated sulfur diimides, K(NSN)R (R = tBu, SiMe3, PtBu2) and K(NSN)K, with various boron chlorides R1 2BCl (R1 = tBu, cpent, Et2N, iPr2N), [CH2N(R1)]2BCl (R1 = Me, nBu, iPr, tBu) and R1R2NBCl2 (R1 = R2 = Et, iPr; R1 = PhCH2, R2 = tBu; R1 = PhCH2, R2 = Ph) lead to the corresponding boryl-substituted sulfur diimides 2 – 8, 9a – 20a, 9b, 11b – 13b, 17b and 15c. The sulfur diimides (Et2N)2B(NSN)SiMe3 (11b) and (iPr2N)2B(NSN)tBu (12a) react with hexachlorodisilane by cleavage of the Si-Si bond to give the new bis(amino)sulfanes 21b and 22a, in which the nitrogen atoms bear additional SiCl3 substituents. A complete NMR spectroscopic study was carried out for the known cyclic sulfur diimide iPr2B(NSN)2BNiPr2 (1). All non-cyclic compounds were studied by 1H, 11B, 13C and 15N NMR at variable temperature aiming for configurational assignment. The 15N NMR data, in particular, suggest that in most cases almost linear N=S−B units are preferred with a perpendicular arrangement of the plane of the boryl group with respect to the NSN plane.
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