Issue 20, 2021

Reductive silylation of polyoxovanadate surfaces using Mashima's reagent

Abstract

Here, we present the first example of reductive silylation for oxygen defect formation at the surface of a polyoxometalate. Upon addition of 1,4-bis(trimethylsilyl)dihydropyrazine (Pyz(SiMe3)2) to [V6O7(OMe)12]1−, quantitative formation of the oxygen-deficient vanadium oxide assembly, [V6O6(OMe)12]1− was observed. Substoichiometric reactions of Pyz(SiMe3)2 with the parent cluster revealed the mechanism of defect formation; addition of 0.5 equiv. of Pyz(SiMe3)2 to [V6O7(OMe)12]1− results in isolation of [V6O6(OSiMe3)(OMe)12]1−. This reactivity was extended to reduced and oxidized forms of the cluster, [V6O7(OMe)12]n (n = 2-, 0), revealing the consequences of modifying the oxidation states of remote transition metal ions on the stability of the siloxide functional group, and thus the extent of reactivity of the cluster surface with Pyz(SiMe3)2. The work offers a new understanding of the mechanisms of surface activation of reducible metal oxides via reductive silylation, and reveals new chemical routes for the formation of oxygen atom vacancies in polyoxometalate ions.

Graphical abstract: Reductive silylation of polyoxovanadate surfaces using Mashima's reagent

Supplementary files

Article information

Article type
Research Article
Submitted
25 Jul 2021
Accepted
18 Aug 2021
First published
19 Aug 2021

Inorg. Chem. Front., 2021,8, 4507-4516

Reductive silylation of polyoxovanadate surfaces using Mashima's reagent

S. Chakraborty and E. M. Matson, Inorg. Chem. Front., 2021, 8, 4507 DOI: 10.1039/D1QI00920F

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