Borotungstate polyoxometalates: multinuclear NMR structural characterization and conversions in solutions

The unique heteropolyanion [H(3)BW(13)O(46)](8-) (BW(13)), previously suggested on the basis of indirect evidence, and protonated lacunary heteropolyanion [HBW(11)O(39)](8-) (BW(11)) have been identified in aqueous solutions at pH 5-7.5 from NMR spectra. The pattern of tungsten-tungsten connectivities based on the analysis of the (2)J(W-O-W) coupling satellites in the (183)W NMR spectrum of BW(11), containing six peaks of relative intensities ～2:2:2:1:2:2, indicates that the latter is the α isomer. The (17)O NMR spectrum confirms the protonated state of the polyanion with the proton delocalized on two out of four terminal O atoms surrounding the tungsten vacancy. The (183)W NMR spectrum of BW(13) contains seven peaks of relative intensities ～2:1:2:2:2:2:2 with additional large couplings due to the connectivity between BW(11) and [W(2)O(7)](2-) fragments. According to the (17)O NMR spectrum, two protons of [BW(13)O(46)H(3)](8-) are delocalized on the two terminal trans O atoms of the dimeric fragment while the third one is linked to its bridging O atom. The conversions of BW(11) and BW(13) in solution were followed by using (183)W NMR spectra at a "fingerprint" level. In the pH range from ～7.5 to 6, BW(11) transforms to BW(13), transforming further to [BW(12)O(40)](5-) (BW(12)) and [B(3)W(39)O(132)H(n)](n-21) (B(3)W(39)) in different ratios. Conversion of BW(13) to BW(12) proceeds through an intermediate complex of suggested composition [BW(11)O(39)·WO(2)](7-). At high acidity (pH ～ 0), B(3)W(39) gradually decomposes into tungstic acid, BW(12) and H(3)BO(3). Polyanion BW(12) persists in the pH range ～0-7.5.