Theoretical Prediction of Divalent Actinide Borozene Complexes

Theoretical Prediction of Divalent Actinide Borozene Complexes

The aromatic boron cluster B<sub>8</sub><sup>2–</sup> (<i>D</i><sub>7<i>h</i></sub>) has similar π bonding to C<sub>6</sub>H<sub>6</sub>, which is named “borozene”. The B<sub>8</sub><sup>2–</sup&...

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Bibliographic Details
Main Authors: Naixin Zhang, Qunyan Wu, Jianhui Lan, Weiqun Shi, Congzhi Wang
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Molecules
Subjects:
actinides
boron cluster
borozene complex
chemical bonding
density functional calculations
Online Access:https://www.mdpi.com/1420-3049/29/23/5815
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Summary:The aromatic boron cluster B<sub>8</sub><sup>2–</sup> (<i>D</i><sub>7<i>h</i></sub>) has similar π bonding to C<sub>6</sub>H<sub>6</sub>, which is named “borozene”. The B<sub>8</sub><sup>2–</sup> ligand has been observed to stabilize monovalent Ln(+I) in <i>C</i><sub>7<i>v</i></sub>-LnB<sub>8</sub><sup>−</sup> (Ln = La, Pr, Tb, Tm, and Yb) borozene complexes. Low-valency actinide complexes have been reported more rarely, and B<sub>8</sub><sup>2–</sup> may be one of the potential ligands. Here, we report a theoretical study on a series of actinide metal-doping octa-boron clusters AnB<sub>8</sub> (An = Pa, U, Np, and Pu). It was found that each species has both half-sandwich and chair-like structures. Except for PaB<sub>8</sub>, the half-sandwich structures of UB<sub>8</sub>, NpB<sub>8</sub>, and PuB<sub>8</sub> are more energetically stable than the chair-like structures, and the half-sandwich clusters of AnB<sub>8</sub> are found to be actinide(II) borozene complexes with the M<sup>II</sup>[B<sub>8</sub><sup>2−</sup>] type. For each of the half-sandwich clusters, the B<sub>8</sub><sup>2−</sup> ligand has σ and π double aromaticity. Various bonding analyses of AnB<sub>8</sub> confirm the covalent interactions between the doped actinide metals and the octa-boron clusters, which further stabilize the complexes and determine the relative stability of AnB<sub>8</sub>. As expected, these complexes show high bond dissociation energies, especially PaB<sub>8</sub> with stronger Pa-B covalent bonds. These results demonstrate that the B<sub>8</sub><sup>2−</sup> doubly aromatic ligand is able to stabilize divalent actinides.
ISSN:1420-3049

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