Exploring the Potential Energy Surface of E2P4 Clusters (E=Group 13 Element): The Quest for Inverse Carbon‐Free Sandwiches. Issue 16 (2nd April 2014)

• Record Type: Journal Article
• Authors: Castro, Abril C.; Osorio, Edison; Cabellos, José Luis; Cerpa, Erick; Matito, Eduard; Solà, Miquel; Swart, Marcel; Merino, Gabriel
• Is Part Of: Chemistry. Volume 20:Issue 16(2014)
• Page Start: 4583
• Page End: 4590
• Publication Date: 2014-04-02
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201304685
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 <italic>D</italic>_{4<italic>h</italic>}‐symmetric inverse‐sandwich structure, but instead prefers a <italic>D</italic>_{2<italic>d</italic>} 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 <italic>D</italic>_{4<italic>h</italic>} inverse‐sandwich structure. The preference for the <italic>D</italic>_{2<italic>d</italic>} isomer for B₂P₄ and <italic>D</italic>_{4<italic>h</italic>} 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.</p> </abstract>