TY - JOUR
T1 - Electron-transfer reactivity in the activation of organic fluorides by bare metal monocations
AU - Harvey, Jeremy N.
AU - Schröder, Detlef
AU - Koch, Wolfram
AU - Danovich, David
AU - Shaik, Sason
AU - Schwarz, Helmut
PY - 1997/7/18
Y1 - 1997/7/18
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0031577255&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(97)00560-5
DO - 10.1016/S0009-2614(97)00560-5
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AN - SCOPUS:0031577255
SN - 0009-2614
VL - 273
SP - 164
EP - 170
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 3-4
ER -