Density functional theory (DFT) calculations on the structures and stabilities of [CnO2n+1]2– and [CnO2n+1]X2 polycarbonates containing chainlike (CO2)n units (n = 2–6; X = H or Li)

Abstract

The structures and stabilities of chainlike (CO2)n (n = 2–6) polycarbonates, where adjacent C atoms are linked by C–O–C bonds, were investigated at the density functional theory (DFT) level (B3PW91/6–311G(2d,p)), including dicarboxylic dianions, [CnO2n+1]2–, and the corresponding acids, [CnO2n+1]H2, and Li salts, [CnO2n+1]Li2. At equilibrium, the most stable systems have Cs, C2, or C2v symmetries. In the gas phase, these dianions are generally metastable with respect to spontaneous ejection of one electron, yet in the presence of counterions they become stabilized, for example, as [CnO2n+1]2–(Li+)2 ion pairs. [CnO2n+1]2– linkages are also stabilized as dicarboxylic acids, [CnO2n+1]H2; we find the latter to have equilibrium conformations of higher symmetry than previously reported in the literature. To the best of our knowledge, none of the [CnO2n+1]X2 (X = Li or H) compounds with n ≥ 2 have been reported in the experimental literature (albeit, the alkyl esters C2O5R2 and C3O7R2 are commercially available). All CO bonds in C2O5X2 to C6O13X2 have single- to double-bond character (≈140–118 pm), indicating that the [CnO2n+1] moieties are held together by strong chemical forces (in contrast to the weakly bound complexes (CO2)n and (CO2)n–, n > 1). Vibrational frequencies were calculated to ensure all conformations were true minima. The IR and Raman intensities show that the high intensity C=O stretching modes (1750 ± 100 cm–1) will help in the spectral characterization of these compounds. Solvation calculations using the polarizable continuum model (PCM) find that C2O52– can be formed via CO32– + CO2 as well as CO3–[Formula: see text], each reaction having ΔG298 < 0 in practically all solvents. This result confirms the experimentally observed large solubility of CO2(g) in molten carbonates, CO3M2 (M = Li, Na, or K). In contrast, starting with n = 2, the reactions [CnO2n+1]2– + CO2 do not proceed spontaneously in any solvent (ΔG298 > 0).