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Alkoxido-Derivatised Lindqvist- and Keggin-Type Polyoxometalates

  • R. John Errington
  • Balamurugan Kandasamy
  • Daniel Lebbie
  • Thompson Izuagie
Chapter
Part of the Structure and Bonding book series (STRUCTURE, volume 176)

Abstract

The targeted application of polyoxometalates (POMs) in catalysis, materials science and biology requires an in-depth understanding of how their properties might be tuned through compositional and structural molecular engineering. In practice, this requires chemical methodologies that enable reliable, systematic manipulation of families of related POMs in conjunction with detailed experimental and theoretical studies. Lindqvist-type hexametalates [LM′M5O18] n provide a convenient platform for systematic studies in which M, M′ and L may be varied, and this chapter gives an overview of the development of versatile synthetic methods and the results of detailed reactivity studies based on alkoxido-derivatised anions [(RO)M′M5O18] n. Solid-state structures and NMR studies of solution reactivities are providing an insight into the effects on bonding and electronic properties of metal and ligand substitution in this family of POMs, and comparisons with the related Keggin-type POMs [(RO)M′PW11O39] n enable an assessment of the effect of the supporting POM structure on the reactivity of the heterometal site. The chapter begins with recent investigations of aggregation in nonaqueous synthesis of POMs from metal alkoxides and the introduction of heterometal sites into the hexametalate framework. Subsequent sections discuss how protonolysis of M′OR bonds can be used in the synthesis of ligand-exchanged anions and also for the generation of highly reactive {M′M5} species in solution.

Keywords

Hydrolysis Keggin Lindqvist Metal alkoxides Polyoxometalates Protonation 

Notes

Acknowledgements

We are grateful to COST Action CM1203 (Polyoxometalate Chemistry for Molecular Nanoscience, PoCheMoN) for funding Short-Term Scientific Missions, the Niger Delta Development Commission for a scholarship to TI, the University of St. Andrews for studentship funding (BK) and to Prof. W. G. Klemperer for support.

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Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  • R. John Errington
    • 1
  • Balamurugan Kandasamy
    • 1
  • Daniel Lebbie
    • 1
  • Thompson Izuagie
    • 1
  1. 1.School of ChemistryNewcastle UniversityNewcastle upon TyneUK

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