Deprotonation of the sp 3 C-H bond of HFC-134a with 1•DMAP was calculated to occur via TS-3 with ∆G ‡ 298K = 27.1 kcal mol -1 . Nucleophilic attack at a fluorine atom of the CF3 group of HFC-134a was calculated to occur via TS-4, ∆G ‡ 298K = 26.5 kcal mol -1 . A concerted pathway involving simultaneous breaking of two sp 3 C-F bonds was also considered but a suitable transition state could be located. In terms of further use of the products from the defluorination of HFCs, we have previously shown that 2 can act as a nucleophilic source of fluoride, capably of fluorinating a small array of highly activated electrophiles. In the case of HFC-134a, the volatile product 1