The solution structures of organic carbonate solvents (ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC)) as electrolyte solutions of LiPF 6 were investigated with FTIR and NMR spectroscopy and DFT computational methods. Both coordinated and uncoordinated solvents are observed by IR spectroscopy, allowing the determination of solvent coordination numbers, which a range from 2 to 5. The predominant species in solution changes as a function of LiPF 6 concentration. At low salt concentrations (<1.2 M), the predominant species is a solvent-separated ion pair, whereas at high salt concentrations (>2.0 M) the predominant species in solution is the contact ion pair. In mixed solvent systems (PC−DMC, PC−DEC, EC−DMC, or EC−DEC), the mixed solvated cations are observed in the presence of high concentrations of uncoordinated cyclic carbonate despite the much larger dielectric constant of the cyclic carbonates than dielectric constant of linear carbonate.

The reaction of Cu(I), Ag(I), and Au(I) salts with carbon monoxide in the presence of weakly coordinating anions led to known and structurally unknown non-classical coinage metal carbonyl complexes [M(CO)n][A] (A = fluorinated alkoxy aluminates). The coinage metal carbonyl complexes [Cu(CO)n(CH2Cl2)m](+)[A](-) (n = 1, 3; m = 4-n), [Au2(CO)2Cl](+)[A](-), [(OC)nM(A)] (M = Cu: n = 2; Ag: n = 1, 2) as well as [(OC)3Cu⋅⋅⋅ClAl(OR(F))3] and [(OC)Au⋅⋅⋅ClAl(OR(F))3] were analyzed with X-ray diffraction and partially IR and Raman spectroscopy. In addition to these structures, crystallographic and spectroscopic evidence for the existence of the tetracarbonyl complex [Cu(CO)4](+)[Al(OR(F))4](-) (R(F) = C(CF3)3) is presented; its formation was analyzed with the help of theoretical investigations and Born-Fajans-Haber cycles. We discuss the limits of structure determinations by routine X-ray diffraction methods with respect to the C-O bond lengths and apply the experimental CO stretching frequencies for the prediction of bond lengths within the carbonyl ligand based on a correlation with calculated data. Moreover, we provide a simple explanation for the reported, partly confusing and scattered CO stretching frequencies of [Cu(I)(CO)n] units.

The synthesis and characterization of Li[O2P{OCH(CF3)2}2] (1) was investigated together with a new synthesis for Li[O2P(OCH2CF3)2] (2). The electrochemical properties of both lithium bis(fluoroalkyl)phosphates were investigated. Compound 2 was prepared by deprotonation of the conjugate acid HO(O)P(OCH2CF3)2 (3), of which the crystal structure was solved. Lithium bis(fluoroalkyl)phosphates 1 and 2 were used to prepare gel electrolytes on the basis of a coordination network held together solely by ionic interactions between the lithium ions and the anions. The preparation of the gel electrolytes produced with 2 and their properties were explored.