Autor segons l'article: Cameron, Jamie M; Vila-Nadal, Laia; Winter, Ross S; Iijima, Fumichika; Carlos Murillo, Juan; Rodriguez-Fortea, Antonio; Oshio, Hiroki; Poblet, Josep M; Cronin, Leroy
Departament: Química Física i Inorgànica
Autor/s de la URV: Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Paraules clau: Water oxidation Silicotungstate Screening model Polyoxometalate clusters Molecular dynamics Mechanism Mass spectrometry Gas-phase Density-functional theory Correlation-energy Chemistry Aqueous-solution
Resum: 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.
Àrees temàtiques: 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
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Identificador de l'autor: 0000-0002-4533-0623 0000-0001-5884-5629
Data d'alta del registre: 2024-10-12
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/jacs.6b02245
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Journal Of The American Chemical Society. 138 (28): 8765-8773
Referència 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 de l'article: 10.1021/jacs.6b02245
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2016
Tipus de publicació: Journal Publications
Repositori URV