Electron-transfer reactivity in the activation of organic fluorides by bare metal monocations

Jeremy N. Harvey*, Detlef Schröder, Wolfram Koch, David Danovich, Sason Shaik, Helmut Schwarz

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

In the gas phase, the bare calcium monocation reacts with organic fluorides, via C-F bond activation to yield CaF+ together with the corresponding radical. Ab initio calculations are used to analyse the mechanism of reaction with fluoromethane. Density-functional calculations lead to underestimated reaction barriers, whereas ACPF and CCSD(T) calculations with large basis sets provide good agreement with experiment. The reaction involves a tightly bonded TS in which an electron is transferred from calcium to carbon; this structured harpoon mechanism highlights the simultaneous importance of electron transfer and of metal-fluorine bonding in reductive defluorination processes.

Original languageEnglish
Pages (from-to)164-170
Number of pages7
JournalChemical Physics Letters
Volume273
Issue number3-4
DOIs
StatePublished - 18 Jul 1997

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