Reaction of a series of HFCs with a main group reagent containing a Mg-Mg bond results in defluorination to form the corresponding magnesium fluoride complex. In the case of 1,1,1,2-tetrafluoroethane (HFC-134a) generation of the fluoride occurs alongside selective formation of 1,1-difluoroethene. DFT calculations have been carried out to better understand the selectivity and compare the barriers for sp C-F bond activation with sp C-H bond activation in this system.
View Article and Find Full Text PDFPerfluoroalkyl substances (PFAS) are pervasive in the environment. The largest single use material within the PFAS compound class is poly(tetrafluoroethylene) (PTFE), a robust and chemically resistant polymer. Despite their widespread use and serious concerns about their role as pollutants, methods for repurposing PFAS are rare.
View Article and Find Full Text PDFFluorinated gases (F-gases) are routinely employed as refrigerants, blowing agents, and electrical insulators. These volatile compounds are potent greenhouse gases and consequently their release to the environment creates a significant contribution to global warming. This review article seeks to summarise: (i) the current applications of F-gases, (ii) the environmental issues caused by F-gases, (iii) current methods of destruction of F-gases and (iv) recent work in the field towards the chemical repurposing of F-gases.
View Article and Find Full Text PDFThe room-temperature activation of SF6, a potent greenhouse gas, is reported using a monovalent aluminium(i) reagent to form well-defined aluminium(iii) fluoride and aluminium(iii) sulfide products. New reactions have been developed to utilise the aluminium(iii) fluoride and aluminium(iii) sulfide as a nucleophilic source of F- and S2- for a range of electrophiles. The overall reaction sequence results in the net transfer of fluorine or sulfur atoms from an environmentally detrimental gas to useful organic products.
View Article and Find Full Text PDFChem Commun (Camb)
November 2020
The rapid, room-temperature defluorosilylation of trifluoromethane, a highly potent greenhouse gas, has been achieved using a simple silyl lithium reagent. An extensive computational mechanistic analysis provides a viable reaction pathway and demonstrates the unexpected electrophilic nature of LiCF. The reaction generates a bench stable fluorinated building block that shows promise as an easy-to-use difluoromethylating agent.
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