The chemistry of NSF3 was mainly developed in three directions: (a) nucleophilic exchange of the sulfur bonded fluorines to give NSFnR3-n ( n=2, R=R2N, Rf, Alk, Ar; n=2, R=Rf and R2N, R=Ar; n=3, R=Ar); (b) addition of Lewis acids to the thiazyl nitrogen and (c) saturation of the triple bond.Recently we have shown that NBO analysis provides a tool to predict the border of the triple bond character in dependence of different ligands1. Mono substituted thiazyls NSF2R are triple bond species, independent of R. Despite of the very short NS bond distances (144 � 147 pm), the di- and tri-substituted aryl derivatives NSFnAr3-n (n=1,0), prepared by Yoshimura et al.2by the oxidative rearrangement of N-fluoro sulfilimines FN=SArAr' to give NSFArAr', and nucleophilic substitution of the fluorine, cannot be regarded as triple bond species.E.g- saturation of the NS bond with coordination expansion of the sulfur is not possible.The ultimate proof for the donor properties of NSF3 towards various Lewis acids (nonmetal cations, metal and organometallic cations ) is the introduction as ligand into Xenon chemistry3. The characterization of intermediates in the Xenon mediated saturation of the NS triple bond from NSF3 to [SF5NH3]+is a key for the understanding of the reaction pathway.The extremely short NS bond in [CH3NSF3]+(136.2(4)pm)4 is surpassed only by the OS triple bond in [OSF3]+(135.8(4) pm)4,5- Similar to the saturation of the NS bond of NSF3 by HF to give HNSF4 and H2NSF5. HF addition to the [OSF3]+ should be possible, resulting in the formation of [HOSF4]+ and [H2OSF5]+.(1.)Mews, R. et al. 17th ESFC, Paris, July 21-25, 2013  , Abstr.IL B10. (2.)Y�shimura, T. et al., Rev.Heteroatom Chem. 2000  ,32, 191. (3.)Schrobilgen, G. et al., Inorg.Chem.2011  , 50, 12359. (4.)Mews, R., Lork, E., Steinke, G. to be published. (5.)Passmore, J. et al., JCS Dalton, 1973  , 2513.

Some general aspects of sulfur-nitrogen and sulfur-oygen triple bonds

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.