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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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Nitrate and Perchlorate Reduction by a Dinuclear Mo(V) Complex.

Shui Ling Chen1, L Taylor Elrod1, Stephen Marriott1

  • 1Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.

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|August 29, 2025
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A novel dinuclear molybdenum catalyst efficiently reduces persistent groundwater contaminants, nitrate and perchlorate. This bioinspired catalyst demonstrates significant potential for environmental remediation applications.

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Area of Science:

  • Coordination Chemistry
  • Environmental Chemistry
  • Catalysis

Background:

  • Nitrate and perchlorate are stable, soluble groundwater contaminants.
  • Microbial reduction of these anions involves molybdenum-containing enzymes.
  • A previously studied monomeric Mo(VI) complex, [Mo^VI O_2(L^Br)(MeOH)] (1), was thought to form an inactive dinuclear Mo(V) byproduct, [Mo_2O_3(L^Br)_2(THF)_2] (2).

Purpose of the Study:

  • To synthesize and characterize the dinuclear Mo(V) complex 2.
  • To investigate the catalytic reactivity of complex 2 with nitrate and perchlorate.
  • To explore the effect of scandium(III) as a cocatalyst in these reactions.

Main Methods:

  • Synthesis and full characterization (spectroscopic, crystallographic) of the dinuclear Mo(V) complex 2.
  • Catalytic studies involving oxygen atom transfer (OAT) reactions with DMSO and PPh3.
  • Evaluation of nitrate and perchlorate reduction catalysis by complex 2, with and without Sc^3+.

Main Results:

  • The dinuclear Mo(V) complex 2 was successfully synthesized and characterized.
  • Contrary to expectations, complex 2 is catalytically active, mediating OAT from DMSO to PPh3.
  • Complex 2 effectively reduces both nitrate (two OAT steps per NO3-) and perchlorate (four OAT steps per ClO4-), yielding N2O and Cl-, respectively.
  • Scandium(III) significantly accelerates perchlorate reduction but has a minor effect on nitrate reduction.

Conclusions:

  • The dinuclear Mo(V) complex 2 is a versatile homogeneous catalyst for oxygen atom transfer reactions.
  • Complex 2 demonstrates significant potential for the reductive remediation of nitrate and perchlorate groundwater contaminants.
  • The catalytic activity of complex 2 challenges previous assumptions about its role as an inactive byproduct.