Defluorination of HFCs by a magnesium reagent.

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 sp3 C-F bond activation with sp3 C-H bond activation in this system.

Room Temperature Defluorination of Poly(tetrafluoroethylene) by a Magnesium Reagent.

Perfluoroalkyl 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. Here we show that a nucleophilic magnesium reagent reacts with PTFE at room temperature, generating a molecular magnesium fluoride which is easily separated from the surface-modified polymer. The fluoride in turn can be used to transfer the fluorine atoms to a small array of compounds. This proof-of-concept study demonstrates that the atomic fluorine content of PTFE can be harvested and reused in chemical synthesis.

Repurposing of F-gases: challenges and opportunities in fluorine chemistry.

Fluorinated 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. There is a great opportunity to tackle the environmental and sustainability issues created by F-gases by developing reactions that repurpose these molecules.

Complete deconstruction of SF6 by an aluminium(I) compound.

The 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.

Defluorosilylation of trifluoromethane: upgrading an environmentally damaging fluorocarbon.

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 LiCF3. The reaction generates a bench stable fluorinated building block that shows promise as an easy-to-use difluoromethylating agent. The difluoromethyl group is an increasingly important bioisostere in active pharmaceutical ingredients, and therefore our methodology creates value from waste. The potential scalability of the process has been demonstrated by achieving the reaction on a gram-scale.