DFT Study on the Oxidation Mechanism of Common Cyclic Carbonates in the Presence of BF 4 - Anions.

Oxidative decomposition reactions of common cyclic carbonates in the presence of BF 4 - anions were investigated using density functional theory. A polarized continuum model was utilized to model solvent effects in the oxidation of ethylene carbonate (EC) and propylene carbonate (PC) clusters. We have found that the presence of BF 4 - significantly reduces EC and PC oxidation stability, from 7.11 to 6.17 and from 7.10 to 6.06 V (vs Li + /Li), respectively. The sequence of EC and PC oxidative decomposition paths and the oxidative products were affected by the BF 4 - anion. The decomposition products of the oxidized EC-BF 4 - contained CO 2 , vinyl alcohol, and acetaldehyde, while the decomposition products of the oxidized PC-BF 4 - contained CO 2 , acetone, and propanal, in agreement with the previous experimental studies. The oxidative decomposition reactions for PC-BF 4 - are compared with those for the isolated PC, PC 2, PC-ClO 4 - , and PC-PF 6 - .