biostudies-literatureUnknown5(6)Mauro LAWe describe the first comparative data on metal-mediated C-H activation and functionalization reactions at two-carbon-atom legacy refrigerants and density functional theory (DFT) analyses on the resulting organometallic products. We reveal that, depending on the degree of fluorination in the refrigerant, C-H activation could lead either to stable M-(H)-R_f products or to a M-(fluoroolefin) complex. The first example of a metal-mediated dehydrofluorination of R-143a is described, resulting from a β-fluoride elimination reaction of a putative [Ir-(H)-(CH₂CF₃)] intermediate and the loss of hydrogen fluoride. This work also reports the first examples of metal-mediated activation of R-125 (CF₃-CF₂H) and R-134a (CF₃-CFH₂ACS organic & inorganic Au518-530https://www.ebi.ac.uk/biostudies/studies/S-EPMC12679306biostudies-literatureIdentifying Reactivity Differences of Two-Carbon-Atom-Based Legacy Refrigerants at Group 9 Metal Pincer Complexes.PMC12679306Mauro LAHerlinger IAHall SJHughes RPCramer REFredin LAVicic DAfalseIdentifying Reactivity Differences of Two-Carbon-Atom-Based Legacy Refrigerants at Group 9 Metal Pincer Complexes.We describe the first comparative data on metal-mediated C-H activation and functionalization reactions at two-carbon-atom legacy refrigerants and density functional theory (DFT) analyses on the resulting organometallic products. We reveal that, depending on the degree of fluorination in the refrigerant, C-H activation could lead either to stable M-(H)-R_f products or to a M-(fluoroolefin) complex. The first example of a metal-mediated dehydrofluorination of R-143a is described, resulting from a β-fluoride elimination reaction of a putative [Ir-(H)-(CH₂CF₃)] intermediate and the loss of hydrogen fluoride. This work also reports the first examples of metal-mediated activation of R-125 (CF₃-CF₂H) and R-134a (CF₃-CFH₂2025-01-01T00:00:00Z2025 Dec2026-06-05T23:27:17.825Z2026-05-23T03:13:31.839ZS-EPMC126793064135645210.1021/acsorginorgau.5c00071