ELECTRON-TRANSFER REACTIVITY IN THE ACTIVATION OF ORGANIC FLUORIDES BY BARE METAL MONOCATIONS (VOL 273, PG 164, 1997)

In the gas phase, the bare calcium monocation reacts with organic fluo rides, via C-F bond activation to yield CaF+ together with the corresp onding radical. Ab initio calculations are used to analyse the mechani sm of reaction with fluoromethane. Density-functional calculations lea d to underestimated reaction barriers, whereas ACPF and CCSD(T) calcul ations with large basis sets provide good agreement with experiment. T he reaction involves a tightly bonded TS in which an electron is trans ferred from calcium to carbon; this structured harpoon mechanism highl ights the simultaneous importance of electron transfer and of metal-fl uorine bonding in reductive defluorination processes. (C) 1997 Publish ed by Elsevier Science B.V.