Articles producció científica> Química Física i Inorgànica

Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics

  • Datos identificativos

    Identificador: PC:1905
    Handle: https://hdl.handle.net/20.500.11797/PC1905
    Autores:
    Antonio Rodríguez-ForteaJamie M. CameronLaia Vilà-NadalRoss S. WinterFumichika IijimaJuan Carlos MurilloHiroki OshioJosep M. PobletLeroy Cronin
    Resumen:
    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.

  • Otros:

    Autor según el artículo: Antonio Rodríguez-Fortea; Jamie M. Cameron; Laia Vilà-Nadal; Ross S. Winter; Fumichika Iijima; Juan Carlos Murillo; Hiroki Oshio; Josep M. Poblet; Leroy Cronin
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: 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
    Palabras clave: mass spectrometry molecular dynamics
    Resumen: 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.
    Grupo de investigación: Química Quàntica
    Áreas temáticas: Chemistry Química Química
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0002-7863
    Identificador del autor: 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
    Fecha de alta del registro: 2016-09-13
    Página final: 8773
    Volumen de revista: 138
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: http://pubs.acs.org/doi/abs/10.1021/jacs.6b02245
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI del artículo: https://doi.org/10.1021/jacs.6b02245
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2016
    Página inicial: 8765
    Tipo de publicación: Article Artículo Article

  • Palabras clave:

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

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