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Nucleophilic Activation of Sulfur Hexafluoride: Metal‐Free, Selective Degradation by Phosphines
Author(s) -
Buß Florenz,
MückLichtenfeld Christian,
Mehlmann Paul,
Dielmann Fabian
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201713206
Subject(s) - phosphine , chemistry , reagent , nucleophile , fluorine , sulfur , sulfur hexafluoride , chalcogen , decomposition , inert , organic chemistry , inorganic chemistry , catalysis
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.