Perfluoroalkylated Arsoranide Salts: Syntheses and Structural Insights

Area of Science:

• Organometallic Chemistry
• Fluorine Chemistry
• Arsenic Chemistry

Background:

• Perfluoroalkylated compounds offer unique properties due to strong carbon-fluorine bonds.
• Arsoranide salts are less explored compared to their phosphonium or stibonium counterparts.
• Understanding the synthesis and stability of these compounds is crucial for advancing hypervalent arsenic chemistry.

Purpose of the Study:

• To synthesize and structurally characterize novel perfluoroalkylated arsoranide salts.
• To investigate the influence of different halide and fluoride ligands on arsoranide salt formation.
• To gain insights into the stability of these perfluoroalkylated arsenic anions.

Main Methods:

• Synthesis of diorganyl and monoorganyl arsoranide salts using various arsenic precursors and tetraphenylphosphonium halide salts.
• Introduction of fluoride ligands using silver fluoride (AgF) and cesium fluoride (CsF).
• Structural characterization of the synthesized salts.
• Quantum chemical calculations to assess anion stability.

Main Results:

• High yields of diorganyl arsoranide salts [PPh4][As(CF3)2I2] and [PPh4][As(C2F5)X2] were achieved.
• Selective formation of Cs[As(C2F5)2F2] using CsF, while AgF led to halide exchange.
• Synthesis of monoorganyl arsoranide salts [PPh4][As(CF3)I3] and [PPh4][As(C2F5)X3].
• Quantum chemical calculations provided initial data on anion stability.

Conclusions:

• The study successfully synthesized a range of perfluoroalkylated arsoranide salts with varying ligands.
• Different fluoride sources exhibit distinct reactivity, enabling selective synthesis pathways.
• The findings contribute to the understanding of hypervalent arsenic compounds and their potential applications.