THEORETICAL-STUDIES OF FLUOROCARBONS .3. PRIMARY, SECONDARY, TERTIARY AND QUATERNARY CENTERS

Quantum chemical calculations are used to examine the differences between fully fluorinated alkanes with primary, secondary, tertiary and quaternary centres. Systems studied include C(CF3)nF4-n (n=0-4), CF3[C(CF3)2]pCF3 (p=1-5), (CF3)2CF[C(CF3)2]q CF(CF3)2 (q=0-3) and CF3CF2[C(CF3)2]rC F2CF3 (r=0-3). In addition we compare systems which react with arenethiolate nucleophiles under mild conditions (e.g. cisperfluorodecalin and perfluoro(methylcyclohexane)) and those which do not (e.g. perfluorohexane and perfluorocyclohexane). A crude "lattice energy" model is used to investigate the likelihood of electron transfer, which is one possible mechanism for the unexpected reactivity. © 1990.