Nucleophilic Activation of Sulfur Hexafluoride: Metal-Free, Selective Degradation by Phosphines
作者:Florenz Buß、Christian Mück-Lichtenfeld、Paul Mehlmann、Fabian Dielmann
DOI:10.1002/anie.201713206
日期:2018.4.23
sulfides and difluorophosphoranes or in the selective conversion of SF6 into a bench‐stable, crystalline salt containing the SF5− anion. Quantum chemical calculations reveal a nucleophilic substitution mechanism (SN2) for the initial fluorine abstraction from SF6 by the phosphine. Furthermore, a scalable one‐pot procedure for the complete decomposition of SF6 into solid, nonvolatile products is presented
极惰性温室气体六氟化硫(SF 6)的化学活化新方法的开发不仅具有当前的环境意义,而且为将SF 6用作有机合成中的试剂提供了新的机会。我们在本文中报道了Lewis碱(即膦)对SF 6的首次亲核活化,这导致其完全降解为磷化氢硫化物和二氟膦或将SF 6选择性转化为稳定的,含有SF 5的结晶盐-阴离子。量子化学计算揭示了一个亲核取代机理(S Ñ2)用于由膦从SF 6初始提取氟。此外,还提出了一种可扩展的一锅法,可根据廉价的市售起始原料将SF 6完全分解为固态,非挥发性产品。