Cameron, J. M., Vilà-Nadal, L. , Winter, R. S., Iijima, F., Murillo, J. C., Rodríguez-Fortea, A., Oshio, H., Poblet, J. M. and Cronin, L. (2016) Investigating the transformations of polyoxoanions using mass spectrometry and molecular dynamics. Journal of the American Chemical Society, 138(28), pp. 8765-8773. (doi: 10.1021/jacs.6b02245) (PMID:27321042)
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Abstract
The reactions of [γ-SiW10O36]8– represent one of the most important synthetic gateways into a vast array of polyoxotungstate chemistry. Herein, we set about exploring the transformation of the lacunary polyoxoanion [β2-SiW11O39]8– into [γ-SiW10O36]8– using high-resolution electrospray mass spectrometry, density functional theory, and molecular dynamics. We show that the reaction proceeds through an unexpected {SiW9} precursor capable of undertaking a direct β → γ isomerization via a rotational transformation. The remarkably low-energy transition state of this transformation could be identified through theoretical calculations. Moreover, we explore the significant role of the countercations for the first time in such studies. This combination of experimental and the theoretical studies can now be used to understand the complex chemical transformations of oxoanions, leading to the design of reactivity by structural control.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Vila-Nadal, Dr Laia and Cameron, Mr Jamie and Winter, Mr Ross and Cronin, Professor Lee |
| Authors: | Cameron, J. M., Vilà-Nadal, L., Winter, R. S., Iijima, F., Murillo, J. C., Rodríguez-Fortea, A., Oshio, H., Poblet, J. M., and Cronin, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| ISSN: | 0002-7863 |
| ISSN (Online): | 1520-5126 |
| Published Online: | 20 June 2016 |
| Copyright Holders: | Copyright © 2016 American Chemical Society |
| First Published: | First published in Journal of the American Chemical Society 138(28):8765-8773 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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