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Nonaqueous Polyoxometalate Synthesis for Systematic Studies of Hydrolysis, Protonation, and Reduction

Lookup NU author(s): Dr John Errington

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Abstract

Dynamic aspects of polyoxometalate chemistry are often overlooked because of difficulties in monitoring subtle structural and/or speciation changes in solution. This chapter features the non-aqueous approaches to polyoxometalate synthesis being developed in our laboratory as a platform for detailed and systematic reactivity studies. Methods based on metal alkoxide hydrolysis are described that provide access to a range of substituted {M2W4} and {MW5} Lindqvist-type polyoxometalates containing reactive {MX}n+ heterometal sites, and examples are given that highlight the importance of 17O NMR as a tool for monitoring solution reactivity. Lindqvist-type {XTiW5} and {XSnW5} and related Keggin-type {XMPW11} anions are compared and significant differences in their hydrolysis and condensation behaviours are discussed in relation to DFT studies. The solution reactivity observed upon halide abstraction from {ClTiW5} or protonation of {(RO)TiW5} species is rationalized in terms of a common di-functional reactive intermediate [TiW5O18]2–, which has been characterized in its dimeric form. Following the identification of di-protonated [(µ-O)(TiW5O18H)2]4– a new type of polyoxometalate ligand behavior is proposed, based on the characterization of [(µ-O)(TiW5O18)2(SnMe2)]4–, 17O NMR studies of reactions with electrophiles and DFT studies of [(µ-O)(TiW5O18)2(AuCl)]4–. The final section describes non-aqueous reductive aggregation reactions of (TBA)3[PMo12O40] that have produced a family of electron-rich anions of the type a-[PMo12O40(MLn)z]x–, and the reductive degradation of (TBA)2[Mo6O19] to give the tetra-capped e-[Mo13O40H4{Mg(dmso)3}4]2+.


Publication metadata

Author(s): Errington RJ

Editor(s): Rudi van Eldik and Leroy Cronin

Publication type: Book Chapter

Publication status: Published

Book Title: Polyoxometalate Chemistry

Year: 2017

Volume: 69

Pages: 287-336

Online publication date: 04/02/2017

Acceptance date: 02/04/2016

Series Title: Advances in Inorganic Chemistry

Publisher: Elsevier

URL: https://doi.org/10.1016/bs.adioch.2016.12.010

DOI: 10.1016/bs.adioch.2016.12.010

Notes: This is an invited Chapter for a thematic issue on "Polyoxometallate Chemistry"

Library holdings: Search Newcastle University Library for this item

ISBN: 9780128111055


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