Ennobling an Old Molecule: Thiazyl Trifluoride (NSF3), a Versatile Synthon for Xe–N Bond Formation

The fields of sulfur-nitrogen-fluorine chemistry and noble-gas chemistry have been significantly extended by the syntheses and characterizations of four new Xe-N-bonded cations derived from N≡SF(3). The adduct-cation, F(3)S≡NXeF(+), has provided the entry point to a significant chemistry through HF solvolysis of the coordinated N≡SF(3) ligand and HF-catalyzed and solid-state rearrangements of F(3)S≡NXeF(+). The HF solvolyses of [F(3)S≡NXeF][AsF(6)] in anhydrous HF (aHF) and aHF/BrF(5) solutions yield the F(4)S═NXe(+) cation, which likely arises from an HF-catalyzed mechanism. The F(4)S═NXe(+) cation, in turn, undergoes HF displacement to form F(4)S═NH(2)(+) and XeF(2), as well as HF addition to the S═N bond to form F(5)SN(H)Xe(+). Both cations undergo further solvolyses in aHF to form the F(5)SNH(3)(+) cation. The F(4)S═NXe(+) and F(4)S═NH(2)(+) cations were characterized by NMR spectroscopy and single-crystal X-ray diffraction and exhibit high barriers to rotation about their S═N double bonds. They are the first cations known to contain the F(4)S═N- group and significantly extend the chemistry of this ligand. The solid-state rearrangement of [F(3)S≡NXeF][AsF(6)] at 22 °C has yielded [F(4)S═NXe][AsF(6)], which was characterized by Raman spectroscopy, providing the first examples of xenon bonded to an imido nitrogen and of the F(4)S═N- group bonded to a noble-gas element. The rearrangement of [F(3)S≡NXeF][AsF(6)] in a N≡SF(3) solution at 0 °C also yielded [F(4)S═NXe−N≡SF(3)][AsF(6)], which represents a rare example of a N−Xe−N linkage and the first to be characterized by X-ray crystallography. Solvolysis of N≡SF(3) in aHF was previously shown to give the primary amine F(5)SNH(2), whereas solvolysis in the superacid medium, AsF(5)/aHF, results in amine protonation to give [F(5)SNH(3)][AsF(6)]. Complete structural characterizations were not available for either species. Isolation of F(5)SNH(2)·nHF from the reaction of N≡SF(3) with HF has provided a structural characterization of F(5)SNH(2) by Raman spectroscopy. Crystal growth by sublimation of F(5)SNH(2)·nHF at -30 to -40 °C has resulted in the X-ray crystal structure of F(5)SNH(2)·2[F(5)SNH(3)][HF(2)]·4HF and structural characterizations of F(5)SNH(2) and F(5)SNH(3)(+). The redox decomposition of [F(4)S═NXe−N≡SF(3)][AsF(6)] in N≡SF(3) at 0 °C generated Xe, cis-N(2)F(2), and [F(3)S(N≡SF(3))(2)][AsF(6)].