Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics

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• 作者：Jamie M. Cameron ; Laia Vilà-Nadal ; Ross S. Winter ; Fumichika Iijima ; Juan Carlos Murillo ; Antonio Rodríguez-Fortea ; Hiroki Oshio ; Josep M. Poblet ; Leroy Cronin
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：July 20, 2016
• 年：2016
• 卷：138
• 期：28
• 页码：8765-8773
• 全文大小：584K
• 年卷期：0
• ISSN：1520-5126

文摘

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.