Reversible Temperature Dependent Dimerization of Transition Metal Substituted Quasi Wells-Dawson Polyfluoroxometalates

Marco Bugnola, Roy E. Schreiber, Yehonatan Kaufman, Gregory Leitus, Linda J.W. Shimon, Ronny Neumann

Research output: Contribution to journalArticle

Abstract

Polyfluoroxometalates (PFOMs) that have a quasi Wells-Dawson structure and have low valent transition metal substitution at the so-called "belt" position, α1-[H2F6NaM(H2O)W17O55]q-, can reversibly interchange between dimeric and monomeric structures. The dimers have two unique M-μO-W bridges between two PFOM units. The dimerization occurs through dehydration and was studied as a function of temperature using the visible spectrum that is sensitive to the wavelength and extinction coefficient of the d-d transition. The calculated thermodynamic parameters of the dimerization reaction were iteratively fitted using a function derived from the equilibrium constant and the Beer-Lambert law. Such reversible dimerization reactions have not been observed for similar α1-[P2M(H2O)W17O61]q- structures, thus fluorine atoms in an axial position to the transition metal are apparently critical for dimerization by reducing the bond strength of the transition metal-aqua bond trans to the fluorine atom.

Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

Dimerization
Transition metals
Fluorine
Atoms
Temperature
Equilibrium constants
Interchanges
Dehydration
Dimers
Substitution reactions
Thermodynamics
Wavelength

Keywords

  • Dimerization
  • Fluorides
  • Oxides
  • Polyoxometalates

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Reversible Temperature Dependent Dimerization of Transition Metal Substituted Quasi Wells-Dawson Polyfluoroxometalates. / Bugnola, Marco; Schreiber, Roy E.; Kaufman, Yehonatan; Leitus, Gregory; Shimon, Linda J.W.; Neumann, Ronny.

In: European Journal of Inorganic Chemistry, 01.01.2018.

Research output: Contribution to journalArticle

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AU - Bugnola, Marco

AU - Schreiber, Roy E.

AU - Kaufman, Yehonatan

AU - Leitus, Gregory

AU - Shimon, Linda J.W.

AU - Neumann, Ronny

PY - 2018/1/1

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N2 - Polyfluoroxometalates (PFOMs) that have a quasi Wells-Dawson structure and have low valent transition metal substitution at the so-called "belt" position, α1-[H2F6NaM(H2O)W17O55]q-, can reversibly interchange between dimeric and monomeric structures. The dimers have two unique M-μO-W bridges between two PFOM units. The dimerization occurs through dehydration and was studied as a function of temperature using the visible spectrum that is sensitive to the wavelength and extinction coefficient of the d-d transition. The calculated thermodynamic parameters of the dimerization reaction were iteratively fitted using a function derived from the equilibrium constant and the Beer-Lambert law. Such reversible dimerization reactions have not been observed for similar α1-[P2M(H2O)W17O61]q- structures, thus fluorine atoms in an axial position to the transition metal are apparently critical for dimerization by reducing the bond strength of the transition metal-aqua bond trans to the fluorine atom.

AB - Polyfluoroxometalates (PFOMs) that have a quasi Wells-Dawson structure and have low valent transition metal substitution at the so-called "belt" position, α1-[H2F6NaM(H2O)W17O55]q-, can reversibly interchange between dimeric and monomeric structures. The dimers have two unique M-μO-W bridges between two PFOM units. The dimerization occurs through dehydration and was studied as a function of temperature using the visible spectrum that is sensitive to the wavelength and extinction coefficient of the d-d transition. The calculated thermodynamic parameters of the dimerization reaction were iteratively fitted using a function derived from the equilibrium constant and the Beer-Lambert law. Such reversible dimerization reactions have not been observed for similar α1-[P2M(H2O)W17O61]q- structures, thus fluorine atoms in an axial position to the transition metal are apparently critical for dimerization by reducing the bond strength of the transition metal-aqua bond trans to the fluorine atom.

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KW - Oxides

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