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Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics.
Cameron, Jamie M; Vilà-Nadal, Laia; Winter, Ross S; Iijima, Fumichika; Murillo, Juan Carlos; Rodríguez-Fortea, Antonio; Oshio, Hiroki; Poblet, Josep M; Cronin, Leroy.
Afiliação
  • Cameron JM; School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
  • Vilà-Nadal L; Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
  • Winter RS; School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
  • Iijima F; School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
  • Murillo JC; Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
  • Rodríguez-Fortea A; Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
  • Oshio H; Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
  • Poblet JM; Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
  • Cronin L; Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
J Am Chem Soc ; 138(28): 8765-73, 2016 07 20.
Article em En | MEDLINE | ID: mdl-27321042
The reactions of [γ-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 [ß2-SiW11O39](8-) into [γ-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 ß â†’ γ 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.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2016 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2016 Tipo de documento: Article