Author, as appears in the 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
Department: Química Física i Inorgànica
URV's Author/s: Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Keywords: Water oxidation Silicotungstate Screening model Polyoxometalate clusters Molecular dynamics Mechanism Mass spectrometry Gas-phase Density-functional theory Correlation-energy Chemistry Aqueous-solution
Abstract: 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.
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
Record's date: 2024-10-12
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.6b02245
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 138 (28): 8765-8773
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
Article's DOI: 10.1021/jacs.6b02245
Entity: Universitat Rovira i Virgili
Journal publication year: 2016
Publication Type: Journal Publications
Repositori URV