Weakly coordinating anions HA2-generated from oxoanions A- and their conjugate acids. Coordination equilibria, ionic conductivities, and the structures of [Cu2(H(CH3SO3)2)4]n and [Cu(CO)(H(CF3CO2)2)]2.

The coordination or ion pairing of the hydrogen-bonded anions H(CF3CO2)2- and H(CH3SO3)2- to NEt4+, Li+, Cu+, and/or Cu2+ was investigated. The structure of [Cu2(H(CH3SO3)2)4]n consists of centrosymmetric dimeric moieties that contain two homoconjugated (CH3SO2O-H...OSO2CH3)- anions per Cu2+ ion, forming typical Jahn-Teller tetragonally elongated CuO6 coordination spheres. The oxygen atoms involved in the nearly linear O-H...O hydrogen bonds (O...O approximately 2.62 A) are not coordinated to the Cu2+ ions. The structure of Cu2(CO)2(H(CF3-CO2)2)2 consists of pseudo-C2-symmetric dimers that contain one homoconjugated (CF3COO-H...OCOCF3)- anion per Cu+ ion, forming highly distorted tetrahedral Cu(CO)O3 coordination spheres. Three of the four oxygen atoms in each hydrogen-bonded H(CF3CO2)2- anion are coordinated to the Cu+ ions, including one of the oxygen atoms in each O-H...O hydrogen bond (O...O approximately 2.62 A). Infrared spectra (v(CO) values) of Cu(CO)(CF3CO2) or Cu(CO)(CH3SO3) dissolved in acetonitrile or benzene, with and without added CF3COOH or CH3SO3H, respectively, demonstrate that HA2- anions involving carboxylates or sulfonates are more weakly coordinating than the parent anions RCO2- and RSO3-. Direct current conductivities of THF solutions of Li(CF3CO2) containing varying concentrations of added CF3COOH further demonstrate that Li+ and NEt4+ ion pair much more weakly with H(CF3CO2)2- than with CF3CO2-.