Exploring the Potential Energy Surface of E₂P₄ Clusters (E=Group 13 Element): The Quest for Inverse Carbon‐Free Sandwiches

Abstract

Inverse carbon-free sandwich structures with formula E2P4 (E=Al, Ga, In, Tl) have been proposed as a promising new target in main-group chemistry. Our computational exploration of their corresponding potential-energy surfaces at the S12h/TZ2P level shows that indeed stable carbon-free inverse-sandwiches can be obtained if one chooses an appropriate Group 13 element for E. The boron analogue B2P4 does not form the D(4h)-symmetric inverse-sandwich structure, but instead prefers a D(2d) structure of two perpendicular BP2 units with the formation of a double B-B bond. For the other elements of Group 13, Al-Tl, the most favorable isomer is the D(4h) inverse-sandwich structure. The preference for the D(2d) isomer for B2P4 and D(4h) for their heavier analogues has been rationalized in terms of an isomerization-energy decomposition analysis, and further corroborated by determination of aromaticity of these species.