Isomerism and Biradical Character of Tetrapnictide Dianions: A Computational Study
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Date
2020-10-08
Publication Type
Journal Article
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Abstract
We present a computational study on tetrapnictide dianions Pn42– (Pn = P, As, Sb, Bi), using density functional theory (DFT), coupled‐cluster [DLPNO‐CCSD(T)] and complete active space self‐consistent field (CASSCF) methods. Environmental effects such as solvation and coordination of counterions are included. The calculations reveal that out of three isomers (square‐planar, butterfly and capped‐triangle), the square planar isomers are generally the most stable. The counterion (Li+ and Mg2+) used in the calculations have a substantial effect on the relative stabilities. The square planar isomers show considerable biradical character. Calculated reactions toward alkenes indicate that this unusual electronic structure has significant implications on the reactivity of the Pn42– dianions.
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published
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Volume
2020 (37)
Pages / Article No.
3580 - 3586
Publisher
Wiley
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Subject
Ab initio calculations; Density functional calculations; Heterocycles; Pnicogens; Radicals
Organisational unit
03447 - Grützmacher, Hansjörg (emeritus) / Grützmacher, Hansjörg (emeritus)