Articles producció científica> Química Física i Inorgànica

Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics

  • Identification data

    Identifier: PC:1905
    Handle: https://hdl.handle.net/20.500.11797/PC1905
    Authors:
    Antonio Rodríguez-ForteaJamie M. CameronLaia Vilà-NadalRoss S. WinterFumichika IijimaJuan Carlos MurilloHiroki OshioJosep M. PobletLeroy Cronin
    Abstract:
    The reactions of [¿-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 [¿2-SiW11O39]8- into [¿-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 ¿ ¿ ¿ 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.

  • Others:

    Author, as appears in the article.: Antonio Rodríguez-Fortea; Jamie M. Cameron; Laia Vilà-Nadal; Ross S. Winter; Fumichika Iijima; Juan Carlos Murillo; Hiroki Oshio; Josep M. Poblet; Leroy Cronin
    Department: Química Física i Inorgànica
    URV's Author/s: RODRÍGUEZ FORTEA, ANTONIO; Jamie M. Cameron; Laia Vilà-Nadal; Ross S. Winter; Fumichika Iijima; Juan Carlos Murillo; Hiroki Oshio; POBLET RIUS, JOSEP MARIA; Leroy Cronin
    Keywords: mass spectrometry molecular dynamics
    Abstract: The reactions of [¿-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 [¿2-SiW11O39]8- into [¿-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 ¿ ¿ ¿ 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.
    Research group: Química Quàntica
    Thematic Areas: Chemistry Química Química
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0002-7863
    Author identifier: 0000-0001-5884-5629; 0000-0003-0138-933X; 0000-0002-7718-7227; n/a; n/a; n/a; n/a; 0000-0002-4533-0623; n/a
    Record's date: 2016-09-13
    Last page: 8773
    Journal volume: 138
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: http://pubs.acs.org/doi/abs/10.1021/jacs.6b02245
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: https://doi.org/10.1021/jacs.6b02245
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    First page: 8765
    Publication Type: Article Artículo Article

  • Keywords:

    Espectrometria de masses
    Dinàmica molecular
    mass spectrometry
    molecular dynamics
    Chemistry
    Química
    Química
    0002-7863

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