Density functional studies of ring-opening reactions of Li+-(ethylene carbonate) and Li+-(vinylene carbonate)

Abstract

Reaction energies were determined for reductive ring-opening reactions of Li+-coordinated ethylene carbonate (EC) and vinylene carbonate (VC) by a density functional method. We have also explored the ring-opening of Li+-EC and Li+-VC by reaction with a nucleophile (CH3O-) thermodynamically. Our thermodynamic calculations led us to conclude that the possible reaction products are CH3OCH2CH2OCO2Li (O-2-C-3 cleavage) for Li+-EC + CH3O-, and CH3OCHCHOCO2Li (O-2-C-3 cleavage) and CH3OCO2CHCHOLi (C-1-O-2 cleavage) for Li+-VC + CH3O-. The opening of VC would occur at the C-1-O-2 side by a kinetic reason, although the opening at the O-2-C-3 side is more favorable thermodynamically.