Nucleophilic Activation of Sulfur Hexafluoride: Metal‐Free, Selective Degradation by Phosphines

Abstract The development of new methods for the chemical activation of the extremely inert greenhouse gas sulfur hexafluoride (SF 6 ) not only is of current environmental interest, but also offers new opportunities for applications of SF 6 as a reagent in organic synthesis. We herein report the first nucleophilic activation of SF 6 by Lewis bases, namely by phosphines, which results either in its complete degradation to phosphine sulfides and difluorophosphoranes or in the selective conversion of SF 6 into a bench‐stable, crystalline salt containing the SF 5 − anion. Quantum chemical calculations reveal a nucleophilic substitution mechanism (S N 2) for the initial fluorine abstraction from SF 6 by the phosphine. Furthermore, a scalable one‐pot procedure for the complete decomposition of SF 6 into solid, nonvolatile products is presented based on cheap and commercially available starting materials.