Structure and Bonding in [M6O19]n-Isopolyanions

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Abstract
The structure and bonding in [M6O19]n- isopolyanions of Nb, Ta, Mo, and W have been investigated using density-functional methods. The computational−experimental agreement is good for the geometrical parameters of Mo and W species but less satisfactory for Nb and Ta clusters. The electronic structure of the anions has been probed with molecular-orbital, Mulliken−Mayer, and bonding-energy approaches. The results have indicated that M−O interactions are largely M d−O p in character and that σ and π bonds link the metal centers to terminal and bridging (Ob) oxygen atoms. Some M−Ob bonds exhibit a [M4O4] closed-loop structure, but this orbital-interaction mode has not been found to make a particularly outstanding contribution to the bonding stability of the molecules. Mayer indexes correspond to (fractional) multiple, approximately single, and low-order character for terminal, bridging, and internal bonds, respectively, and the valency analysis has yielded similar bonding capacities for the different oxygen atoms. A distribution of the negative charge over all types of oxygen sites and metal charges considerably smaller than the formal oxidation states have been obtained from the Mulliken analysis. Minimal structural changes have been detected on reduction of molybdates and tungstates, in accord with the general properties of the orbitals occupied by the added electrons.