Estimation of free energies of anion transfer from solid-state electrochemistry of alkynyl-based Au(I) dinuclear and Au(I)-Cu(I) cluster complexes containing ferrocenyl groups

摘要

A method is presented to determine the free energy for anion transfer between two solvents. This is based on solid-state electrochemistry of alkynyl-based dinuclear Au(I) complexes (AuC2R)2PPh 2C6H4PPh2 (L1: R = Fc; L2: R = C6H4Fc) and heterometallic Au(I)-Cu(I) [{Au 3Cu2 (C2R)6}Au3(PPh 2C6H4PPh2)3](PF 6)2 (L3: R = Fc; L4: R = C6H4Fc) complexes. These compounds exhibit a reversible ferrocenyl-centred solid-state oxidation processes involving anion insertion in contact with aqueous, MeOH and MeCN electrolytes. Voltammetric data can be used for a direct measurement of the free energy of ion transfer using midpeak potentials in solutions of suitable salts in the solvents separately or in mixtures of the solvents.