Zheng, Q., Vila-Nadal, L. , Busche, C. , Mathieson, J. S., Long, D.-L. and Cronin, L. (2015) Following the reaction of heteroanions inside a {W18O56} polyoxometalate nanocage by NMR spectroscopy and mass spectrometry. Angewandte Chemie (International Edition), 127(27), pp. 8006-8010. (doi: 10.1002/ange.201502295)
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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.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Busche, Dr Christopher and Long, Dr Deliang and Mathieson, Dr Jennifer and Vila-Nadal, Dr Laia and Cronin, Professor Lee |
| Authors: | Zheng, Q., Vila-Nadal, L., Busche, C., Mathieson, J. S., Long, D.-L., and Cronin, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Angewandte Chemie (International Edition) |
| Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA |
| ISSN: | 1433-7851 |
| ISSN (Online): | 1521-3757 |
| Copyright Holders: | Copyright © 2015 The Authors |
| First Published: | First published in Angewandte Chemie (International Edition) 127(27):8006-8010 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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