CO2 capture has attracted increasing attention owing to its contribution to global warming and climate change as a greenhouse gas. As an alternative strategy to transition-metal-based chemistry and catalysis, frustrated Lewis pairs have been developed to sequester CO2 efficiently under mild conditions. However, the mechanism of CO2 sequestration with amidophosphoranes remains unclear. Herein, we present a thorough density functional theory study on a series of amidophosphoranes. Our results reveal that the interplay of the ring strain and the trans influence determines the reactivities, thus opening a new avenue to the design of frustrated Lewis pairs for CO2 capture.

http://onlinelibrary.wiley.com/doi/10.1002/asia.201300864/abstract