Autor según el artículo: Cameron, Jamie M; Vila-Nadal, Laia; Winter, Ross S; Iijima, Fumichika; Carlos Murillo, Juan; Rodriguez-Fortea, Antonio; Oshio, Hiroki; Poblet, Josep M; Cronin, Leroy
Departamento: Química Física i Inorgànica
Autor/es de la URV: Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Palabras clave: Water oxidation Silicotungstate Screening model Polyoxometalate clusters Molecular dynamics Mechanism Mass spectrometry Gas-phase Density-functional theory Correlation-energy Chemistry Aqueous-solution
Resumen: The reactions of [gamma-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 [beta(2)-SiW11O39](8-) into [gamma-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 beta -> gamma 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.
Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Identificador del autor: 0000-0002-4533-0623 0000-0001-5884-5629
Fecha de alta del registro: 2024-10-12
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jacs.6b02245
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Journal Of The American Chemical Society. 138 (28): 8765-8773
Referencia de l'ítem segons les normes APA: Cameron, Jamie M; Vila-Nadal, Laia; Winter, Ross S; Iijima, Fumichika; Carlos Murillo, Juan; Rodriguez-Fortea, Antonio; Oshio, Hiroki; Poblet, Josep M (2016). Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics. Journal Of The American Chemical Society, 138(28), 8765-8773. DOI: 10.1021/jacs.6b02245
DOI del artículo: 10.1021/jacs.6b02245
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2016
Tipo de publicación: Journal Publications
Repositori URV