Ennobling an Old Molecule: Thiazyl Trifluoride (NSF<sub>3</sub>), 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<sub>3</sub>. The adduct-cation, F<sub>3</sub>SNXeF<sup>+</sup>, has provided the entry point to a significant chemistry through HF solvolysis of the coordinated NSF<sub>3</sub> ligand and HF-catalyzed and solid-state rearrangements of F<sub>3</sub>SNXeF<sup>+</sup>. The HF solvolyses of [F<sub>3</sub>SNXeF][AsF<sub>6</sub>] in anhydrous HF (aHF) and aHF/BrF<sub>5</sub> solutions yield the F<sub>4</sub>SNXe<sup>+</sup> cation, which likely arises from an HF-catalyzed mechanism. The F<sub>4</sub>SNXe<sup>+</sup> cation, in turn, undergoes HF displacement to form F<sub>4</sub>SNH<sub>2</sub><sup>+</sup> and XeF<sub>2</sub>, as well as HF addition to the SN bond to form F<sub>5</sub>SN(H)Xe<sup>+</sup>. Both cations undergo further solvolyses in aHF to form the F<sub>5</sub>SNH<sub>3</sub><sup>+</sup> cation. The F<sub>4</sub>SNXe<sup>+</sup> and F<sub>4</sub>SNH<sub>2</sub><sup>+</sup> 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<sub>4</sub>SN– group and significantly extend the chemistry of this ligand. The solid-state rearrangement of [F<sub>3</sub>SNXeF][AsF<sub>6</sub>] at 22 °C has yielded [F<sub>4</sub>SNXe][AsF<sub>6</sub>], which was characterized by Raman spectroscopy, providing the first examples of xenon bonded to an imido nitrogen and of the F<sub>4</sub>SN– group bonded to a noble-gas element. The rearrangement of [F<sub>3</sub>SNXeF][AsF<sub>6</sub>] in a NSF<sub>3</sub> solution at 0 °C also yielded [F<sub>4</sub>SNXe---NSF<sub>3</sub>][AsF<sub>6</sub>], 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<sub>3</sub> in aHF was previously shown to give the primary amine F<sub>5</sub>SNH<sub>2</sub>, whereas solvolysis in the superacid medium, AsF<sub>5</sub>/aHF, results in amine protonation to give [F<sub>5</sub>SNH<sub>3</sub>][AsF<sub>6</sub>]. Complete structural characterizations were not available for either species. Isolation of F<sub>5</sub>SNH<sub>2</sub>·<i>n</i>HF from the reaction of NSF<sub>3</sub> with HF has provided a structural characterization of F<sub>5</sub>SNH<sub>2</sub> by Raman spectroscopy. Crystal growth by sublimation of F<sub>5</sub>SNH<sub>2</sub>·<i>n</i>HF at −30 to −40 °C has resulted in the X-ray crystal structure of F<sub>5</sub>SNH<sub>2</sub>·2[F<sub>5</sub>SNH<sub>3</sub>][HF<sub>2</sub>]·4HF and structural characterizations of F<sub>5</sub>SNH<sub>2</sub> and F<sub>5</sub>SNH<sub>3</sub><sup>+</sup>. The redox decomposition of [F<sub>4</sub>SNXe---NSF<sub>3</sub>][AsF<sub>6</sub>] in NSF<sub>3</sub> at 0 °C generated Xe, <i>cis</i>-N<sub>2</sub>F<sub>2</sub>, and [F<sub>3</sub>S(NSF<sub>3</sub>)<sub>2</sub>][AsF<sub>6</sub>].

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.