Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry |
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| Authors: | Qi Zheng Dr Laia Vilà‐Nadal Dr Christoph Busche Dr Jennifer S Mathieson Dr De‐Liang Long Prof Dr Leroy Cronin |
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| Institution: | WestCHEM, School of Chemistry, The University of Glasgow, Glasgow G12 8QQ (UK) http://www.croninlab.com |
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| Abstract: | By incorporating phosphorus(III)‐based anions into a polyoxometalate cage, a new type of tungsten‐based unconventional Dawson‐like cluster, W18O56(HPIIIO3)2(H2O)2]8?, was isolated, in which the reaction of the two phosphite anions HPO3]2? within the {W18O56} cage could be followed spectroscopically. As well as full X‐ray crystallographic analysis, we studied the reactivity of the cluster using both solution‐state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH???HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two PIII template moieties to form PV centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells–Dawson {W18O54} cluster. |
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| Keywords: | cluster compounds electronic structure NMR spectroscopy phosphorus polyoxometalates |
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