Peer-reviewedCC BY 4.0Inorganic Chemistry14 Oct 2026

M(IV)- and M(V)-Substituted {MW5} Lindqvist-Type Polyoxometalates from Plenary [W6O19]2– or WO3·H2O: A Gateway to Wider Systematic Reactivity Studies

Dominic Shiels¹
Daniel Lebbie¹
Amar Mohammed¹
Magda Pascual-Borràs^1,2
Rosie Black¹
Corinne Wills³
Paul G. Waddell³
Benjamin R. Horrocks³
R. John Errington¹

¹NUPOM Lab, Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K.
²Departament de Química Inorgànica i Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain
³Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K.

Abstract

The reactivity of polyoxometalates (POMs) may be tuned by heterometal substitution into the POM framework, and systematic reactivity studies of these nanoscale molecular metal oxide structures require reliable, efficient synthetic methods. We have now shown that nonaqueous base degradation of either WO3·H2O or plenary (TBA)2[W6O19] (TBA)2 1 followed by reaction with heterometal precursors provides convenient, high-yield access to MIV- and MV-substituted {MW5} Lindqvist-type hexametalates [(iPrO)TiW5O18]3– 2, [(MeO)MW5O18]3– (M = Ti 3, Sn 4), [{(MeO)MW5O18}2]6– (M = Zr 5, Hf 6) and [MW5O19]3– (M = V 7, Nb 8, Ta 9). Crystal structures of (TBA)6 5 and (TBA)6 6 showed the anions to be isostructural, and kinetic studies of CD3OD exchange revealed slightly slower exchange at Hf than Zr. For 5, DFT analysis of MeOH exchange revealed a transition state involving a six-membered ring via insertion of MeOH into a Zr(μ-OMe)Zr bridge. Alkoxide protonolysis reactions provided monomeric {LMW5} derivatives with 7-coordinate Zr or Hf, and X-ray crystal structures of (TBA)3[(PhCO2)ZrW5O18] (TBA)3 12, (TBA)3[(PhCO2)HfW5O18] (TBA)3 13 and (TBA)3[(acac)HfW5O18] (TBA)3 14 were obtained. Cyclic voltammetry showed one-electron couples for 3, 4, 7, 8, and 9 but not for dimeric 5 and 6, consistent with calculated reduction potentials for these {MW5} anions.

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BibTeX RIS

BibTeX

@article{shiels2026mvsubstituted,
  title = {{M(IV)- and M(V)-Substituted MW5 Lindqvist-Type Polyoxometalates from Plenary [W6O19]2– or WO3·H2O: A Gateway to Wider Systematic Reactivity Studies}},
  author = {Dominic Shiels and Daniel Lebbie and Amar Mohammed and Magda Pascual-Borràs and Rosie Black and Corinne Wills and Paul G. Waddell and Benjamin R. Horrocks and R. John Errington},
  journal = {Inorganic Chemistry},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.inorgchem.6c03884},
  url = {https://doi.org/10.1021/acs.inorgchem.6c03884},
  note = {CC BY 4.0},
}

RIS

TY  - JOUR
TI  - M(IV)- and M(V)-Substituted {MW5} Lindqvist-Type Polyoxometalates from Plenary [W6O19]2– or WO3·H2O: A Gateway to Wider Systematic Reactivity Studies
AU  - Dominic Shiels
AU  - Daniel Lebbie
AU  - Amar Mohammed
AU  - Magda Pascual-Borràs
AU  - Rosie Black
AU  - Corinne Wills
AU  - Paul G. Waddell
AU  - Benjamin R. Horrocks
AU  - R. John Errington
PY  - 2026
DA  - 2026/10/14
JO  - Inorganic Chemistry
DO  - 10.1021/acs.inorgchem.6c03884
UR  - https://doi.org/10.1021/acs.inorgchem.6c03884
AB  - The reactivity of polyoxometalates (POMs) may be tuned by heterometal substitution into the POM framework, and systematic reactivity studies of these nanoscale molecular metal oxide structures require reliable, efficient synthetic methods. We have now shown that nonaqueous base degradation of either WO3·H2O or plenary (TBA)2[W6O19] (TBA)2 1 followed by reaction with heterometal precursors provides convenient, high-yield access to MIV- and MV-substituted {MW5} Lindqvist-type hexametalates [(iPrO)TiW5O18]3– 2, [(MeO)MW5O18]3– (M = Ti 3, Sn 4), [{(MeO)MW5O18}2]6– (M = Zr 5, Hf 6) and [MW5O19]3– (M = V 7, Nb 8, Ta 9). Crystal structures of (TBA)6 5 and (TBA)6 6 showed the anions to be isostructural, and kinetic studies of CD3OD exchange revealed slightly slower exchange at Hf than Zr. For 5, DFT analysis of MeOH exchange revealed a transition state involving a six-membered ring via insertion of MeOH into a Zr(μ-OMe)Zr bridge. Alkoxide protonolysis reactions provided monomeric {LMW5} derivatives with 7-coordinate Zr or Hf, and X-ray crystal structures of (TBA)3[(PhCO2)ZrW5O18] (TBA)3 12, (TBA)3[(PhCO2)HfW5O18] (TBA)3 13 and (TBA)3[(acac)HfW5O18] (TBA)3 14 were obtained. Cyclic voltammetry showed one-electron couples for 3, 4, 7, 8, and 9 but not for dimeric 5 and 6, consistent with calculated reduction potentials for these {MW5} anions.
SN  - 0020-1669
SN  - 1520-510X
ER  -

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