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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Isomerism in Complexes
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Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Revisiting the Three Vanadium Sandwich-Type Polyoxometalates: Structures, Solution Behavior, and Redox Properties.

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This study details the synthesis and characterization of oxidized sandwich-type polyoxometalates. These compounds exhibit stability across a pH range and undergo selective electrochemical oxidation, offering insights into their redox properties.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Electrochemistry

Background:

  • Trivacant anions α-B-[XW9O33]9- react with vanadyl ions to form sandwich-type polyoxometalates.
  • Oxidized derivatives of these polyoxometalates are selectively obtained via electrochemical oxidation.

Purpose of the Study:

  • To synthesize and fully characterize oxidized sandwich-type polyoxometalates.
  • To investigate the structural, solution, and redox properties of these compounds.
  • To compare the behavior of arsenic- and antimony-containing derivatives.

Main Methods:

  • Electrochemical oxidation
  • UV-vis spectroscopy
  • Multinuclear NMR spectroscopy (17O, 51V, 183W)
  • Single-crystal X-ray diffraction
  • pH stability studies

Main Results:

  • Selective electrochemical oxidation yielded characterized oxidized polyoxometalates with D3 symmetry.
  • These compounds demonstrated good hydrolytic stability in the pH range of 0-6.
  • As-containing polyanions converted from C2 to D3 forms upon heating, while Sb-containing derivatives exclusively formed D3 structures.
  • Electrochemical studies revealed one-electron transfer per {V=O} group, with redox properties influenced by pH (0.3-5).

Conclusions:

  • Oxidized sandwich-type polyoxometalates are structurally well-defined and possess notable hydrolytic stability.
  • The nature of the heterogroup (As vs. Sb) influences the structural outcome and stability.
  • Proton-coupled electron transfer mechanisms are implicated in the observed redox behavior within a specific pH range.