Quantitative measure for the "nakedness" of fluoride ion sources

A quantitative measure for the donor strength or "nakedness" of fluoride ion donors is presented. It is based on the free energy change associated with the transfer of a fluoride ion from the donor to a given acceptor molecule. Born-Haber cycle calculations were used to calculate both the free energy and the enthalpy change for this process. The enthalpy change is given by the sum of the fluoride ion affinity of the acceptor (as defined in strict thermodynamic convention) and the lattice energy difference (DeltaU(POT)) between the fluoride ion donor and the salt formed with the acceptor. Because, for a given acceptor, the fluoride affinity has a constant value, the relative enthalpy (and also the corresponding free energy) changes are governed exclusively by the lattice energy differences. In this study, BF3, PF5, AsF5, and SbF5 were used as the acceptors, and the following seven fluoride ion donors were evaluated: CsF, N(CH3)(4)F (TMAF), N-methylurotropinium fluoride (MUF), hexamethylguanidinium fluoride (HMGF), hexamethylpiperidinium fluoride (HMPF), N,N,N-trimethyl-1-adamantylammonium fluoride (TMAAF), and hexakis(dimethylamino)phosphazenium fluoride (HDMAPF). Smooth relationships between the enthalpy changes and the molar volumes of the donor cations were found which asymptotically approach constant values for infinitely large cations. Whereas CsF is a relatively poor F- donor [(U-POT(CsF) - U-POT(CsSbF6)) = 213 kJ mol(-1)], when compared to N(CH3)(4)F [(UPOT(TMAF) - UPOT(TMASbF(6))) = 69 kJ mol(-1)], a 4 times larger cation (phosphazenium salt) and an infinitely large cation are required to decrease DeltaU(POT) to 17 and 0 kJ mol(-1), respectively. These results clearly demonstrate that very little is gained by increasing the cation size past a certain level and that secondary factors, such as chemical and physical properties, become overriding considerations.