Exploring the potential energy surface of E₂P₄ clusters (E=Group 13 element): the quest for inverse carbon-free sandwiches.
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.
Institut de Química Computacional i Catàlisi and Dept. de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona, Catalonia (Spain); Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Km 6 Antigua Carretera a Progreso. Apdo. Postal 73, Cordemex, 97310, Mérida, Yuc. (México).
Abril C
AC
Castro
Edison
E
Osorio
José Luis
JL
Cabellos
Erick
E
Cerpa
Eduard
E
Matito
Miquel
M
Solà
Marcel
M
Swart
Gabriel
G
Merino
aromaticity; cluster compounds; computational chemistry; coordination chemistry; density functional theory; main group chemistry