J. Pacansky et Rj. Waltman, THE EFFECT OF LEWIS-ACID CATALYSIS ON THE DECOMPOSITION OF CF3OCF3 TOCOF2 AND CF4, Journal of fluorine chemistry, 83(1), 1997, pp. 41-45
The CF3OCF3 and AlF3 Lewis acid interaction is investigated by ab init
io theory to explain the catalytically enhanced degradation of polyper
fluorinated ether lubricants. Thus, an understanding of the Lewis acid
interaction in these materials is gained by investigating the optimiz
ed geometries of CF3OCF3 in the presence and absence of AlF3. The comp
uted bond parameters and partial atomic charges identify a strong inte
raction between the aluminum substrate and the CF3OCF3 ether oxygen at
om. A transition state that connects the reactant CF3OCF3 and products
COF2 and CF4 is identified. The effect of the Lewis acid interaction
on the transition state geometry is analyzed. A significant reduction
in the activation energy to the transition state via the Lewis acid in
teraction is computed, providing a quantitative understanding for cata
lytically induced degradation in these materials. (C) 1997 Elsevier Sc
ience S.A.