Assessing Fluorosulfonyl Pentafluorooxosulfate (FSO₂-OSF₅) Reservoir Capacity: Selective SOF₄, SO₂F₂, and [OSF₅]^-...

Area of Science:

• Inorganic Chemistry
• Fluorine Chemistry
• Sulfur Chemistry

Background:

• The pentafluorooxosulfate (OSF₅) moiety is a key functional group in sulfur-fluorine chemistry.
• Development of stable and reactive reagents for OSF₅ chemistry is crucial for synthetic applications.

Purpose of the Study:

• To present the synthesis and characterization of novel inorganic reagents containing the OSF₅ group.
• To explore the reactivity and applications of these new reagents in chemical synthesis.
• To investigate the SuFEx (Sulfur(VI) Fluoride Exchange) reactivity of the synthesized compounds.

Main Methods:

• Gram-scale preparation of pentafluorosulfur hypofluorite (FOSF₅).
• Synthesis and characterization of fluorosulfonyl pentafluorooxosulfate (FSO₃SF₅, FSPO) via fluoro-pentafluorooxosulfanylation of SO₂.
• Spectroscopic analysis (NMR, IR, etc.) for full characterization.
• Investigation of in-solution release of OSF₅ ion-pairs, SOF₄, and SO₂F₂.
• Exploration of SuFEx reactivity for one-pot synthesis of sulfonyl fluoride and sulfurimidoyl fluoride species.

Main Results:

• Successful gram-scale preparation of reactive yet stable FOSF₅.
• Characterization of FSPO, a liquid reagent (b.p. 39.6 °C).
• Demonstrated modulable release of [cat][OSF₅] ion-pair from FSPO.
• Selective in-solution release of SOF₄ and SOF₄/SO₂F₂ species was achieved.
• Investigated SuFEx reactivity, showing reservoir ability for one-pot synthesis of -SO₂F and ─N═S(O)F₂.

Conclusions:

• Novel inorganic reagents containing the OSF₅ moiety have been successfully synthesized and characterized.
• These reagents offer controlled release capabilities for OSF₅ and related species.
• The developed compounds exhibit promising SuFEx reactivity, enabling efficient one-pot syntheses.