Isomerism and Biradical Character of Tetrapnictide Dianions: A Computational Study
Open access
Date
2020-10-08Type
- Journal Article
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. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000443787Publication status
publishedExternal links
Journal / series
European Journal of Inorganic ChemistryVolume
Pages / Article No.
Publisher
WileySubject
Ab initio calculations; Density functional calculations; Heterocycles; Pnicogens; RadicalsOrganisational unit
03447 - Grützmacher, Hansjörg (emeritus) / Grützmacher, Hansjörg (emeritus)
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