Investigating the Transformations of Polyoxoanions Using Mass Spectrometry and Molecular Dynamics.
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 [β2-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 β → 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.
School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.|Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
Jamie M
JM
Cameron
School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
Laia
L
Vilà-Nadal
School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
Ross S
RS
Winter
Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
Fumichika
F
Iijima
Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
Juan Carlos
JC
Murillo
Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
Antonio
A
Rodríguez-Fortea
Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba , Tennodai 1-1-1, Tsukuba 305-8571, Japan.
Hiroki
H
Oshio
Departament de Química Física i Inorgànica, Marcel·lí Domingo 1, Universitat Rovira i Virgili , Tarragona, Spain 43007.
Josep M
JM
Poblet
School of Chemistry, WestCHEM, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
Leroy
L
Cronin