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DFT study of α-Keggin, lacunary Keggin, and iron(II–VI) substituted Keggin polyoxometalates: the effect of oxidation state and axial ligand on geometry, electronic structures and oxygen transfer
Herein, the geometry, electronic structure, Fe–ligand bonding nature and simulated IR spectrum of α-Keggin, lacunary Keggin, iron(ii/iii)-substituted and the important oxidized high-valent iron derivatives of Keggin type polyoxometalates have been studied using the density functional theory (DFT/OPT...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9056712/ https://www.ncbi.nlm.nih.gov/pubmed/35519024 http://dx.doi.org/10.1039/d0ra05189f |
Sumario: | Herein, the geometry, electronic structure, Fe–ligand bonding nature and simulated IR spectrum of α-Keggin, lacunary Keggin, iron(ii/iii)-substituted and the important oxidized high-valent iron derivatives of Keggin type polyoxometalates have been studied using the density functional theory (DFT/OPTX-PBE) method and natural bond orbital (NBO) analysis. The effects of different Fe oxidation states (ii–vi) and H(2)O/OH(−)/O(2−) ligand interactions have been addressed concerning their geometry and electronic structures. It has been revealed that the d-atomic orbitals of Fe and 2p orbitals of polyoxometalate's oxygen-atoms contribute in ligand binding. Compared with other high valent species, the considered polyoxometalate system of [PW(11)O(39)(Fe(V)O)](4−), possesses a high reactivity for oxygen transfer. |
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