Abstract
The rate coefficients and anion product branching ratios for the thermal (300 K) reactions of O2− , O−, OH−, CF3− , and F− with SeF6 and TeF6 are reported. Non-dissociative and dissociative electron transfer pathways are identified, together with F+ abstraction and association. F− does not react with SeF6 ; all the other reactions proceed at or close to the capture rate. This is in contrast to SF6 , for which the only observed reaction with the above anions is slow (k = 3.0 × 10−11 cm3 molecule−1 s−1) electron transfer with O2− to form SF6− . The results are shown to be consistent with the available thermochemistry. There is evidence for a substantial intrinsic barrier to F+ abstraction, for this pathway is only observed when it is highly exothermic. There is a remarkably fast association reaction between F− and TeF6 , arising from the high fluoride affinity of TeF6 and facile expansion of the Te co-ordination sphere to accommodate seven ligands.
Published Version
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