6533b870fe1ef96bd12cfd44

RESEARCH PRODUCT

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

Antonio DoménechIgor O. KoshevoyNoemí MontoyaTapani A. Pakkanen

subject

Aqueous solutionChemistryInorganic chemistrySolvationElectrolyteElectrochemistryIonlcsh:Chemistrychemistry.chemical_compoundlcsh:Industrial electrochemistrylcsh:QD1-999ElectrochemistryThermochemistryPhysical chemistryThermochemical cycleMetallocenelcsh:TP250-261

description

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)2PPh2C6H4PPh2 (L1: R=Fc; L2: R=C6H4Fc) and heterometallic Au(I)–Cu(I) [{Au3Cu2 (C2R)6}Au3(PPh2C6H4PPh2)3](PF6)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. Keywords: Ion solvation, Thermochemistry, Electrochemical anion insertion, Alkynyl metal complexes, Heterometallic clusters, Ferrocenyl units

yearjournalcountryeditionlanguage
2011-01-01Electrochemistry Communications
10.1016/j.elecom.2010.11.023http://www.sciencedirect.com/science/article/pii/S1388248110004972