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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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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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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
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Supramolecular Association between γ-Cyclodextrin and Preyssler-Type Polyoxotungstate.

Nathalie Leclerc1, Mohamed Haouas1, Clément Falaise1

  • 1Institut Lavoisier de Versailles, UMR 8180 CNRS, UVSQ, Université Paris-Saclay, 78035 Versailles, France.

Molecules (Basel, Switzerland)
|September 10, 2021
PubMed
Summary

Researchers created a novel hybrid material by combining polyoxometalates and gamma-cyclodextrin (γ-CD). This supramolecular compound, NaP•1CD, exhibits weak interactions between its inorganic and organic components in solution.

Keywords:
NMR spectroscopyXRD structurecyclic voltammetryelectrochemical impedance spectroscopypolyoxometalatesupramolecular adduct

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High Resolution Physical Characterization of Single Metallic Nanoparticles
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Area of Science:

  • Materials Science
  • Supramolecular Chemistry
  • Inorganic Chemistry

Background:

  • Polyoxometalates (POMs) are versatile inorganic clusters with tunable properties.
  • Hybrid materials offer multifunctional characteristics by integrating different chemical entities.
  • Cyclodextrins (CDs) are cyclic oligosaccharides capable of forming inclusion complexes.

Purpose of the Study:

  • To synthesize and characterize a novel hybrid material integrating a polyoxometalate with gamma-cyclodextrin (γ-CD).
  • To investigate the structural and electronic interactions between the inorganic POM anion and the organic γ-CD molecule in both solid and solution states.

Main Methods:

  • Single-crystal X-ray diffraction for solid-state structural determination.
  • IR-spectroscopy, thermogravimetric analysis, and elemental analysis for compound characterization.
  • Solution studies using cyclic voltammetry, electrochemical impedance spectroscopy, 1H NMR, and 31P DOSY to probe interactions.

Main Results:

  • Crystallization of a supramolecular compound K6Na8{[NaP5W30O110]•(C48H80O40)}•23H2O (NaP•1CD) was achieved.
  • Structural analysis confirmed the formation of a 1:1 adduct between the [NaP5W30O110]14- anion and γ-CD in the solid state.
  • Solution studies indicated weak interactions between the polyoxometalate anion and the γ-CD molecule.

Conclusions:

  • The synthesis successfully yielded a hybrid supramolecular material incorporating polyoxometalates and cyclodextrins.
  • The study demonstrates the formation of a defined adduct in the solid state and weak interactions in solution.
  • This work contributes to the design of novel multifunctional hybrid materials based on POMs and organic hosts.