Investigating the transformations of polyoxoanions using mass spectrometry and molecular dynamics

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 Leroy
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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