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Computational modeling of di-transition-metal-substituted γ-Keggin polyoxometalate anions. Structural refinement of the protonated divacant lacunary silicodecatungstate

Inorganic Chemistry, ISSN: 0020-1669, Vol: 43, Issue: 24, Page: 7702-7708
2004
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Article Description

The B3LYP density functional method has been validated for the di-Mn-substituted γ-Keggin polyoxometalate (POM) anion, [(SiO )Mn(OH)WO ], and for the divacant lacunary silicodecatungastate, γ-[(SiO)WO]. This approach was shown to adequately describe the geometries of [(SiO )Mn(OH)WO ] and γ-[(SiO)WO ]. Three different geometrical models, "full", "medium", and "small", for Mn -γ-Keggin have also been validated. It was shown that the medium [(SiO)Mn(OH)W OH] model, as well as small [(SiO)Mn(OH)W OH] model, preserves structural features of the full system, [(SiO)Mn(OH)WO]. However, the small model distorts the charge distribution at the "active site" of the system and should be used with caution. The same computational approach was employed to elucidate the structure of the di-Fe-substituted γ-Keggin POM. The structure of the acidic (tetra-protonated form) of lacunary POM, γ-[(SiO)WOH] , was shown to be γ-[(SiO)WO (OH)] with four terminal hydroxo ligands, rather than γ-[(SiO)WO(H O)] with two aqua and two oxo(terminal) ligands as reported by Mizuno and co-workers (Science 2003, 300, 964). The observed and calculated asymmetry in the W-O(terminal) bond distances of γ-[(SiO)WOH] is explained in terms of the existence of OH ⋯OH and OH ⋯OH hydrogen-bonding patterns in the γ-[(SiO)WO(OH)] structure.

Bibliographic Details

Musaev, Djamaladdin G; Morokuma, Keiji; Geletii, Yurii V; Hill, Craig L

American Chemical Society (ACS)

Chemistry

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