| Autor: |
Peluzo BMTC; Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, United States., Moura RT Jr; Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, United States.; Department of Chemistry and Physics, Center of Agrarian Sciences, Federal University of Paraiba, 58397-000 Areia, Paraiba, Brazil., Kraka E; Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2024 Nov 25; Vol. 63 (47), pp. 22445-22463. Date of Electronic Publication: 2024 Nov 12. |
| DOI: |
10.1021/acs.inorgchem.4c03348 |
| Abstrakt: |
This study employed relativistic methods to investigate the connection between the conformation and bonding properties of 45 lanthanide trihalides LnX 3 (Ln: La-Lu; X:F, Cl, Br). Our findings reveal several insights. The proper symmetry exhibited by open-shell LnX 3 requires the inclusion of spin-orbit coupling, achieved with 2-component relativistic Hamiltonians. Fluorines (LnF 3 ) primarily exhibit pyramidal structures, while chlorides and bromides tend to yield planar conformations. For a given halide, the strength of Ln-X bonds increases across the lanthanide series, another outcome of the lanthanide contraction. Both strength and covalency of Ln-X bonds decrease upon the halide, i.e., LnF 3 > LnCl 3 > LnBr 3 . We introduced a novel parameter, the local force constant associated with the dihedral β(X-Ln-X-X), k a (β), which quantifies the resistance of these molecules to conformational changes. We observed a correlation between k a (β) and the covalency of the Ln-X bond, with higher k a (β) values indicating a stronger covalent character. Finally, the degree of pyramidalization in the LnX 3 structures is connected to (i) the extent of charge donation within the molecule and (ii) the greater covalency of the Ln-X bond. These findings provide valuable insights into the interplay between the electronic structure and molecular geometry in LnX 3 . |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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